The Selecao looked nervous early on and Real Madrid defender Marcelo put the ball into his own goal to hand Niko Kovac’s men an 11th-minute lead but, with the hosts struggling in front of an expectant crowd, it was the Barcelona star who came to the rescue.
He equalised with a 29th-minute drive, with Croatia goalkeeper Stipe Pletikosa slow to react, and then gave Brazil the lead from the penalty spot after Japanese referee Yuichi Nishimura controversially pointed to the spot, deciding that Dejan Lovren had fouled Fred inside the area. Oscar then made the points safe late on to give the hosts a flattering margin of victory.
"It was the best [opening match I could hope for]," Neymar told ESPN Brasil. "We wanted to win and starting a World Cup with two goals gives me great happiness.
"If you notice the goals, they were all a bit strange. I really did mean to put the ball between the defender's legs [for the first] but not for the shot to be as weak as it was but the important thing is that it was a goal.
"How do I keep my cool for the penalty? It's a lot of practice, to hit the ball really strong. Their keeper gave me a little scare there but the ball went in, thankfully."
Neymar was a touch fortunate to only see a yellow card for a first-half elbow on Real Madrid midfielder Luka Modric but the Barcelona forward says that the caution will not hinder him in the remaining group games.
"I will play naturally. I won't be thinking about it. If I do, it's worse," he added. "Receiving a yellow card on your first match is hard. My elbow hit Modric and I wanted to apologise because I didn't notice he was there.
"If the referee thought there was intention on my part, he was right to give me the yellow but there wasn't."