But he never got to take a spot kick in the shootout that Croatia won 4-2 to move into the semi-finals.
Pre-tournament favourites Brazil must now wait at least another four years to win their sixth World Cup — their last dates back to 2002.
“I am psychologically destroyed. It is definitely the defeat which has hurt me the most, which left me paralysed for ten minutes after the match, after which I burst into tears without being able to stop,” Neymar said in an Instagram message.
“It is going to hurt for a very long time, unfortunately,” he added.
Neymar said immediately after Brazil crashed out that he might have played his last match for his country — but Pele urged him to “keep inspiring us.”
The 82-year-old said on Instagram he hoped the superstar forward would carry on playing, adding that goalscoring achievements were no match for the honour of representing Brazil.