Nuno Gomes scored the all-important goal to send Portugal into the quarter-finals of Euro 2004 and set up a possible date with England.
The tournament hosts beat their Iberian rivals for the first time in 23 years to send them crashing out and allow Greece, who were beaten on the night by Russia, to become surprise qualifiers from Group A.
For Spain, it was yet another failure in a big tournament despite boasting some of the top players in the world.
Coach Inaki Saez had decided to start with Atletico Madrid striker Fernando Torres in preference to Fernando Morientes, despite the latter's terrific season at Monaco and the fact he scored against Greece in their previous game.
Portugal had got their tournament off to a nightmare start, losing to Greece but they hit back with a nervous victory against Russia and came into this game knowing they had to win to progress.
Coach Luiz Felipe Scolari, who faced England in the last eight of the World Cup two years ago as Brazil boss, proved why he is one of the top tacticians in the game by bringing on Nuno Gomes for Pauleta at the re-start and the player
netting after six minutes.
Spain were under intense pressure right from the start with the hosts determined to get an early lead
With only six minutes played, Swedish referee Anders Frisk showed his first yellow card after a clear handball from Pauleta, who will miss the next game.
Too many unforced errors from a nervy Spanish side allowed their rivals to dominate the opening minutes but Scolari's team were unable to get past Spain's
strong rearguard.
In the 14th minute, Spain had their first opportunity with Valencia winger Vicente firing across the goal but an unmarked Torres was unable to provide the finish.
Six minutes later, Spain goalkeeper Iker Casillas was forced to dive to his left following Miguel's powerful effort from the right of the area.
Midway through the first half, Portuguese goalkeeper Ricardo was forced to come off his line to clear a dangerous ball by Raul towards Torres. But Spain
were slowly getting a grip in midfield.
Vicente's formidable run down the left saw him find an unmarked Raul but the striker was unable to test Ricardo after being heavily marked by two defenders.
Seconds later, defender Ivan Helguera came close to surprising the hosts with his right-footed strike going narrowly wide of Ricardo's right post.
One minute before the break, Spain came close to taking the lead after Helguera headed high over the bar following Xabi Alonso's corner.
Portugal replied with Cristiano Ronaldo heading wide a fantastic cross from Luis Figo that ended a breathtaking first half with the goalless scoreline only
favouring the Spaniards.
Scolari made his first move at the re-start in an attempt to get the all-important goal, with Nuno Gomes replacing an anonymous Pauleta.
With 56 minutes played, the prayers of a whole nation were answered as the substitute gave his team the lead to send the Portuguese crowd wild. The Benfica striker got past Albelda and fired a formidable strike towards the left post with Iker Casillas unable to save.
At the other end, Vicente's left-footed cross forced Ricardo to come off his line but the ball went over his head and Raul failed to take advantage with his
header going wide.
Torres should have levelled after he got rid of two defenders only for his powerful shot to strike Ricardo's right post.
The goalscorer was booked for a foul before Saez made his first substitutionw ith midfielder Ruben Baraja replacing Albelda.
Casillas twice denied Portugal a second goal of the evening after his fantastic dive to the left following Figo's powerful free-kick and then when he
cleared Costinha's powerful header on target.
Spain attempted to find the equaliser and had two glorious chances in the 74th minute. Costinha was forced to make a vital clearance with Raul's close-range
loop on target going over Ricardo.
Seconds later, Juanito's angled header from the left of the area struck the crossbar.
Portugal captain Figo received a warm ovation as he left the pitch with Benfica's Petit taking his place in midfield.
And with 10 minutes remaining, Saez brought on Morientes with Juanito coming off while for the hosts, veteran defender Fernando Couto replaced Ronaldo.
Time was running out for Spain who surged forward but were unable to find a good finish and it was Portugal who were proving more dangerous on the break.
With two minutes remaining, Deco's cross found an unmarked Costinha inside the area but his poor header was aimed high over the bar.
Seconds later, Maniche should have sealed it for Portugal but his strike was cleared off the line by Raul Bravo.
However, time had run out for Spain and the party got under way in the Portuguese capital.
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