Spain were two points behind the French having drawn with them at home earlier in qualifying, following a 1-1 draw at home to Finland.
But the Spanish silenced any doubters as Pedro tapped in the winner early in the second half to secure a crucial win.
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The reputation of the Premier League means it is the most popular and one of the most watched leagues in the world.
Five English clubs will compete in the last sixteen of the Champions League for the first time ever as Liverpool, Manchester United, Manchester City, Chelsea and Tottenham face some difficult away matches.