Thousands of Spanish fans make the short journey across the border hoping that their side can finally live up to their potential and set the country on course for its first major trophy since the 1964 European Championship.
Russia are aiming to end a miserable run in European Championships in which they have failed to win any of their last seven matches. That poor run started when the country, then part of the Soviet Union, lost the 1988 final to the Dutch.
Spain's main concern will be to improve on their early form at Euro 2000, when they lost their opener against Norway and only just managed to make the quarter-finals.
"The most important thing is to win the first game," striker Raul said. "That way, the morale in the camp will stay high."
Raul will be partnered up front by Fernando Morientes, who has scored 22 goals in 33 appearances for Spain and is back in form after a successful loan spell at Monaco.
Russia have had problems in their preparations and an end to their winless streak would be a surprise.
Centre-backs
Left back Dmitry Sennikov and playmaker Dmitry Loskov are both nursing injuries and that could mean a reshuffle, with midfielder Alexei Smertin dropping back into central defence.
Coach Georgy Yartsev has indicated he would be happy to take a point from the match.
"For me, any result apart from a defeat would be positive," he told reporters.
Probable teams:
Spain: 23-Iker Casillas; 5-Carles Puyol, 3-Carlos Marchena, 6-Ivan Helguera, 15-Raul Bravo; 17-Joseba Etxeberria, 4-David Albelda, 8-Ruben Baraja, 14-Vicente; 10-Fernando Morientes, 7-Raul.
Russia: 1-Sergei Ovchinnikov; 16-Vadim Yevseyev, 4-Alexei Smertin, 13-Roman Sharonov, 17-Dmitry Sennikov; 22-Yevgeny Aldonin, 15-Dmitry Alenichev, 10-Alexander Mostovoi, 7-Marat Izmailov; 3-Dmitry Sychev, 9-Dmitry Bulykin
Referee: Urs Meier (Switzerland)
Assistant referee: Francesco Buragina, Rudolf Kappeli