Nico Williams climbed off the bench to score the winner as Athletic Bilbao came from behind to beat Atletico Madrid 2-1 and reach the Supercopa de Espana final at King Fahd Stadium.
Atleti looked set to face city rivals Real Madrid in the final after Unai Simon's unfortunate own goal put them in front in the second half.
But Athletic mounted a fightback, Yeray Alvarez equalising and substitute Williams completing the comeback with nine minutes to play in Riyadh, where Jose Maria Gimenez saw red late on.
The holders and LaLiga leaders Madrid will do battle for the first trophy of the season on Sunday.
Joao Felix had the ball in the back of the net only eight seconds into the semi-final, but the Portugal forward had strayed offside.
Atleti wanted a penalty when Thomas Lemar went down under a challenge from Alex Berenguer, but referee Guillermo Cuadra Fernandez and the VAR saw nothing untoward before Jan Oblak denied Inaki Williams at the other end.
Yannick Carrasco let fly from long range, but his venomous drive was straight at Athletic goalkeeper Simon in a first half that fizzled out after a bright start.
The LaLiga champions were in front just after the hour-mark, Joao Felix rising to meet an outswinging corner from Lemar and seeing his header strike an upright before hitting Simon and creeping over the line.
Inigo Martinez came close to an equaliser when Oblak kept out his powerful header, but Alvarez levelled after 77 minutes, leaping to head Iker Muniain's corner home.
Athletic had the momentum and Oblak produced a great save to deny Williams, but the teenager put his side ahead by slotting in with his left foot when Atleti failed to deal with another corner.
Gimenez was given his marching orders following a VAR check right at the end for a dangerous high challenge on Martinez as Atleti crashed out.
Girona 0-1 Villarreal: Traore strike lifts Yellow Submarine
Bertrand Traore's goal gave Villarreal a 1-0 win at Girona on Tuesday that prevented the hosts from reclaiming second spot in LaLiga.
Girona, who have enjoyed a superb campaign, are third with 75 points, trailing Barcelona, who moved a point clear with a 2-0 home win over Real Sociedad on Monday.
Alexander Sorloth and Goncalo Guedes went close for Villarreal in the first half, but Girona goalkeeper Paulo Gazzaniga was in fine form.
Traore broke the deadlock in the 59th minute after latching on to a superb pass from Guedes, however.
Viktor Tsyhankov, Savio and Artem Dovbyk all went close for Girona, but could not find the back of Filip Jorgensen's net.
Villarreal were reduced to 10 men in the 95th minute after Kiko Femenia was sent off for a second yellow card after a push on Aleix Garcia.
Data Debrief: Rare home loss for Girona
Girona have suffered only their second defeat at Montilivi in LaLiga this season, following a 0-3 loss to Real Madrid in September.
The home side attempted 749 passes in this game, their highest total in a single match in LaLiga this season.
Postecoglou rues missed chances against City as Son squanders decisive opportunity
Ange Postecoglou was left to rue missed chances as Tottenham's Champions League hopes were ended after Tuesday's 2-0 defeat to Manchester City.
Spurs needed three points to take the Premier League's top-four race to the final day but were undone by Pep Guardiola's side, who moved within touching distance of another top-flight title.
Erling Haaland's routine tap-in from Kevin De Bruyne's brilliance after 51 minutes proved a cruel blow before the City striker's stoppage-time penalty sealed a decisive three points.
It could have been a different story, though, if Stefan Ortega – on as a second-half substitute for Ederson – did not deny Heung-min Son's gilt-edged chance following Manuel Akanji's error.
The City goalkeeper denied the onrushing Spurs forward when one-on-one with the visitors 1-0 up, and Postecoglou acknowledged his side failed to seize their opportunities.
"We lost the game so it was a missed chance for three points," the frustrated Tottenham manager told Sky Sports.
"We had the opportunities and we had to punish them. It was a tight game and in the big moments we were not able to capitalise and they were.
"I thought we were in the game the whole time, even at 1-0 we had a great chance to go level.
"In the second half we were chasing the game so they got a little more space but I thought we were well in it up until that point [the second goal]."
Spurs' loss proved Aston Villa's gain as Unai Emery's side qualified for the Champions League for the first time in their history, ending a 41-year absence after last featuring in the European Cup in 1982-83.
Postecoglou found it hard to seek the immediate positives, having watched Tottenham fall short and inadvertently damage rivals Arsenal's title hopes in the process.
"We lost the game so I am disappointed," the Australian added, before responding to whether any pride could be taken.
"Not right now because we have lost. We will assess the season, still one more game to go, one more game against Sheffield United and we need to make sure we win.
"I think wherever you finish is a fair reflection of where you are at."
Tottenham will finish outside the top four for the fourth time in the last five seasons, after finishing in the Champions League spots in Mauricio Pochettino’s final four full campaigns in charge (2015-16 to 2018-19).
Postecoglou acknowledged there is still work to do to catch up with England's perennial champions City.
Asked how his side measure up to Guardiola's men, he said: Nothing earth-shattering that I didn't know before the game. We still have some work to do. We need to do some work to catch up."
Real Madrid 5-0 Alaves: Vinicius double continues LaLiga champions party
Vinicius Junior scored twice as newly-crowned LaLiga champions Real Madrid thrashed visitors Alaves 5-0 on Tuesday, after the hosts had paraded the trophy in front of the home fans before the game.
Jude Bellingham and Vinicius scored a goal each inside 30 minutes before Federico Valverde put Los Blancos 3-0 up at the break, unleashing an unstoppable shot into the roof of the net in first-half stoppage time.
Vinicius added one more in the 70th minute from a precise cross by Bellingham that the Brazilian fired into the top corner, and substitute Arda Guler completed the scoring with a low finish.
Carlo Ancelotti's side travel to Villarreal on Sunday before hosting Real Betis on May 25 ahead of their Champions League final against Borussia Dortmund on June 1.
Having thrashed Granada 4-0 on Saturday and Cadiz 3-0, either side of their Champions League semi-final victory over Bayern, Real are firing on all fronts heading into the Wembley Stadium showpiece.
Meanwhile, Alavez remain 11th in the table heading into their next game against Getafe at home on Saturday.
Data Debrief: Madrid capitalise on opportunities
Madrid found the back of the net five times from just 2.47 expected goals (xG), suggesting Los Blancos' finishing quality was far greater than Alaves' 1.28 xG.
Ancelotti's side have now kept 20 clean sheets in 36 LaLiga games this campaign, their most in a single season in the competition's history (19 in the 1986-87, 1987-88 and 2019-20 seasons).
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