SL Benfica twice came from behind before two second-half strikes from Eusébio gave them a stunning win in an eight-goal thriller to retain the European Champion Clubs' Cup.
Ferenc Puskás took his tally in finals in this competition to seven in just two appearances, but each time the lead was pegged back as José Águas, Domiciano Cavém and Mário Coluna all hit the target.
With 18 minutes of the second half completed, the brilliant Eusébio picked himself up to edge the holders ahead from the penalty spot, before completing the scoring with a rasping drive five minutes later. For the first time in six finals, Madrid were beaten.
The young Mozambique-born striker was one of only two new faces in the side from the one that defeated Madrid's great rivals FC Barcelona 3-2 in the previous year's final, when Águas scored an important equaliser soon after Benfica conceded.
The captain was again on target in Amsterdam, scoring immediately after Puskás had followed his 17th-minute opener with a fierce shot from outside the box to establish a two-goal lead for the Blancos on 25 minutes.
Cavém levelled the scores on 34 minutes, but the veteran Hungarian Puskás edged Madrid ahead again just four minutes later when he completed his second hat-trick in two finals.
The Spanish champions managed to hold that lead for almost 13 minutes before Coluna – who was also on target in the 1961 final – once again restored parity. By this time, much of the momentum was with Benfica, who appeared much fitter than their opponents.
Madrid were spearheaded by two 35-year-olds, Puskás and Alfredo Di Stéfano, and following a first half reminiscent of their unbeatable form in the first five editions of the competition, they began to lag after the interval.
Benfica, meanwhile, were lead by two 20-year-old strikers – Coluna and Eusébio – and with Pedro Casado limping heavily at right-back for Madrid, the pair began to dominate.
Eusébio made it 4-3 from the spot on 63 minutes and five minutes later, the youngster ensured the Portuguese side retained the trophy with a sublime long-range strike.
It was to be the last time this great Madrid side was seen in European competition and although they returned the following year after securing the Spanish title, they had lost a number of old faces.