Shevchenko teams up with Andriy Voronin to head the Ukrainian attack, with veteran striker Serhiy Rebrov as a substitute.
Schevchenko's fitness was in doubt until the last moment before game. The newly signed Chelsea striker has been recovering from a knee injury he picked up in May, the AP reports.
Spain coach Luis Aragones, hoping to extend a 22-game unbeaten streak, left Raul out of the lineup as expected, opting instead for a three-pronged attack with Fernando Torres, Luis Garcia and David Villa, who scored 25 goals for Valencia this season.
Russia has deployed two armies and three units of Airborne Forces to its western borders as part of a verification check, Russian Defense Minister Sergei Shoygu said