Goals in each half from Xabi Alonso, on his 100th international appearance, sent the world and European champions into a semi-final with Iberian rivals Portugal in the same Donbass Arena stadium on Wednesday.
While Spain can now contemplate the prospect of facing the in-form Cristiano Ronaldo, France return home after fulfilling their objective of reaching the last eight, only to fall short against the world's top national side.
"Is a quarter-final the level where France is at the moment? I don't know, what I do know is that the best sides will be in the semi-finals and France won't be," said France coach Laurent Blanc.
Spain coach Vicente del Bosque, meanwhile, elected to deploy Barcelona midfielder Cesc Fabregas instead of Fernando Torres at the centre of a fluid attacking configuration.
Abandoning their usual possession-focused approach, France retreated and allowed Spain to take the initiative, and Fabregas had an early penalty appeal turned down after his heels were clipped by Gael Clichy.
With two right-backs on the pitch, France's right flank should have been impregnable, but it was from a move down the left that Spain went ahead in the 14th minute.
Andres Iniesta released Jordi Alba and he held off the stumbling Debuchy to cross for the unmarked Alonso, whose downward header gave the number 14 a 14th international goal.
One such raid drew a free-kick in an advantageous position, and Spain goalkeeper Iker Casillas did well to touch Yohan Cabaye's subsequent attempt over the crossbar.
The low number of fans supporting the two teams made for a subdued atmosphere, while the closest Spain came to extending their lead before half-time was a Gerard Pique header that looped well over.
The start of the second half was similarly muted. Debuchy headed over from Franck Ribery's dinked cross, while Hugo Lloris had to race to the edge of his box to claw the ball away from Fabregas at the other end.
Blanc introduced Samir Nasri, Jeremy Menez and Olivier Giroud from the bench, but still the men in the all-white change strip were unable to capitalise on the promising openings they procured.
There were few scares for Spain in the final 10 minutes, and they made sure of victory in injury time when Alonso swept home a penalty after Reveillere had bundled substitute Pedro Rodriguez to the deck.
It will come as scant consolation to France, but they will not have long to wait for revenge.
The sides are due to meet again in a qualifying match for the 2014 World Cup in Spain on October 16.