The second Nations Cup had a much bigger turn-out than the maiden competition, with England and Italy among those agreeing to enter for the first time, though West Germany would still not take part.
Greece pulled out after being given a first round draw against neighbouring Albania - they refused to play as the countries had officially been at war for 50 years.
England did not make it over the first hurdle, losing 6-3 on aggregate against France, and of the home nations, only Northern Ireland made it to the second round, where they were accounted for by Spain.
The Republic of Ireland were Spain's next victims and that gave the Spaniards a chance to host matters from the semi-final stages onwards.
The Soviet Union ended Italy's chances in round two en route to the semis, while Hungary - first round conquerors of Wales - also joined the Nations Cup elite in Spain.
Denmark made up the quartet after what would be considered a bye to the last four in modern football terms with victories over Malta, Albania and Luxembourg, though they took three matches to beat Luxembourg by a solitary goal.
The Danes found the defending champions waiting for them in Barcelona and the Soviet Union were simply in a different class.
Valeri Voronine, Victor Ponedelnik and Valentin Ivanov were the scorers as they made it back to the final with a 3-0 victory, though in truth it could have been many more.
The other semi-final saw two teams much closer to each other in terms of potential, with Hungary and Spain both possessing some of the most skilful players in Europe at the time.
ENGLAND IN EUROPE: 1964
Beaten in qualifier
1st qual round results
England 1-1 France
France 5-2 England
The Spanish talisman Luis Suarez was not fully fit, but still managed to have a hand in setting up the opening goal for Jesus María Pereda.
There were only six minutes left on the clock when the talented Ferenc Bene scored an opportunistic equaliser and extra-time was required.
Roared on by their home fans in the Bernabeu Stadium, Spain withstood the pace better in an energy-sapping 30 minutes and winger Amancio Amaro eventually got the winner.
The final match-up was laden with political significance - hosts Spain, who had refused to play the Soviet Union at the last Nations Cup, taking on the same side in front of the all-powerful man who had insisted they step aside, General Franco.
He was among a crowd of just under 80,000 and things could not have looked brighter for the Spaniards after Jesus Maria Pereda took just six minutes to find an opening and beat Lev Yashin.
But home optimism did not last long and Galimzian Khusainov equalised with a free-kick.
It stayed 1-1 until the 84th minute when Marcelino Martínez headed in the decisive goal that settled the final in Spain's favour.
1964 Nations Cup results (Held in Spain)
Soviet Union 3-0 Denmark
Spain 2-1 Hungary
Third place play-off
Hungary 3-1 Denmark
Spain 2-1 Soviet Union