The Barcelona striker said he would support Aecio Neves in Sunday's run-off ballot against incumbent Dilma Rousseff.
"I really identify with his proposals for Brazil," Neymar said in a short statement posted on YouTube.
The message came hours after Dunga named Neymar captain of the side and banned earrings, flip-flops and caps while the playes are on international duty and restricted use of cellphones and iPads during meals and team talks.
Neymar, 22, made his feelings clear about the restriction on taking political stance.
"We shouldn't be afraid to take a position, it's our democratic right to choose a candidate," he said.
Neymar, who is expected to play in this weekend's Real Madrid-Barcelona match, is the second footballing celebrity to declare support for Neves after Ronaldo.
(Reporting by Andrew Downie; Editing by Amlan Chakraborty)
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