The hosts went ahead in the 66th minute with a thumping low strike from forward Hugo Duro, who spent last season on loan with Madrid.
Real levelled with a deflected strike from Vinicius in the 86th minute and then the Brazilian turned provider, crossing for Benzema to head home the winner in the 88th. Valencia would have gone top of LaLiga had they held on for the win but instead Carlo Ancelotti's Real side lead the standings with 13 points from five games.
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