The reigning champion began the campaign to defend their title, by beating Serbiaby 3-1 in Benidorm.
Spain's title defence had got off to a slow start after high winds had caused damage to the temporary stands and court erected in Benidorm, causing Friday's two singles matches to be postponed until Saturday.
When they were finally played, the Spanish romped to a 2-0 lead after David Ferrer beat Serbia's best player Novak Djokovic 6-3, 6-3, 7-6 and World number one Rafael Nadal raced past Janko Tipsarevic 6-1, 6-0. 6-2.
A win in the doubles gave the Serbs a glimmer of hope for Sunday's remaining singles matches, but Nadal ended their hopes with a straight sets win over Djokovic 6-4, 6-4, 6-1.
Spain will now play Germany in the last eight.
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