The Barcelona forward converted a hotly disputed spot-kick 19 minutes from time after Fred tumbled under minimal contact from Dejan Lovren.
It capped a superb night for the 22-year-old on a personal level as he marked his 50th cap for his country by drilling in a low 25-yard effort just shy of the half hour after Niko Kovac's side had silenced a buoyant home crowd.
The team nicknamed Vatreni started well and stunned the stadium on 11 minutes when Real Madrid defender, Marcelo put through his own net after Nikica Jelavic had failed to connect with Ivica Olic's left-wing cross.
But Neymar led the response and after the controversial late penalty, Chelsea's Oscar raced clear and sealed it with a toe-poke in injury time.
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