Serero gave the home side the lead after 19 minutes when he drilled home from Lasse Schone's cross.
Minutes earlier, Barca nearly took the lead when Neymar's blocked shot fell to Cesc Fabregas, but the Spain international was unable to convert as his shot deflected wide.
Barca were almost back in it after 25 minutes when Neymar beat the offside trap to go through, but the Brazilian's effort was eventually closed down.
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As the first half petered out, Hoesen converted via a deflection off Gerard Pique to give the Dutch side an unlikely two-goal lead.
Xavi converted from the spot to give Gerardo Martino's side a route back into the game, but the Dutch side held on to give their qualification hopes a shot in the arm.