The 23-year-old was appointed captain of Dunga's side in the aftermath of World Cup 2014, but was criticised for allowing his emotions to get the better of him at this summer's Copa America.
Neymar was sent off following the group stage defeat to Colombia after headbutting Jeison Murillo and was consequently handed a four-match ban, which ruled him out of the rest of the tournament.
Leonardo - who has previously been vocal in his criticism of the Barcelona forward - has now repeated his concerns over the player's temperament.
He told SporTV: "Neymar is a great player, but he doesn't have the maturity to lead Brazil and take the team by his hand."
Leonardo did, however, point to the former Santos star's improvement since leaving his homeland for Barcelona in the summer of 2013: "I criticised him a lot when he played in Brazil.
"He took the ball and only wanted to dribble with it and make the difference. Today, he can also play without the ball. I didn't think he could do that - it is a question of mentality.
"Previously he didn't take free-kicks. Now, he's a big threat from set-pieces. There are a multitude of things a great player can improve on."
Neymar scored 39 goals in 51 games in all competitions for Barca as they won a European and domestic treble under Luis Enrique.
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