The Blaugrana forward scored his side's sixth, adding to goals from Adriano, Alexis Sanchez, Pedro and two from Lionel Messi, as the Catalans recorded a comfortable 6-0 win over the Madrid-based outfit.
Neymar has not featured since suffering an ankle injury a month ago - since then Sandro Rosell resigned as club president due to external pressure over the behind-the-scenes details of the Brazilian's move Camp Nou last summer.
The 22-year-old expressed his satisfaction at being able to take to the pitch again, though, and was delighted that his comeback was topped with an impressive, long-distance effort.
"I'm very happy to be able to play and I'm very happy that I scored," Neymar told reporters after the game.
"This month has been long, I was very eager to play. [For the performance] I'd give the team a nine out of 10. We played a really good game, but you can always improve."
The victory saw Barcelona reclaim top spot in La Liga from Atletico Madrid, who had beaten Real Valladolid 3-0 earlier on Saturday, and Pedro echoed Neymar's thoughts on the quality of his team's display as they look forward to their midweek Champions League clash with Manchester City."We played a good match and the build-up that ended in my goal was beautiful," the Spain winger said.
"This victory gives us confidence for the difficult games ahead. During the season we've played some good games, but today we played one of the best games of the season.
"The game on Tuesday against City will be a very difficult match."
Barcelona will travel to face City on Tuesday in the first leg of their Champions League last-16 tie.