Scolari guided Brazil to their fifth World Cup in 2002, and has been tasked with winning it again on home soil in 2014 having replaced Mano Menezes late last year.
The first game of the 64-year-old's second spell in charge is the prestigious friendly against England at Wembley on Wednesday night, with Neymar expected to be part of a strong starting line-up.
Neymar's only previous encounters with the Brazil coach have come while playing for Santos against Palmeiras when Scolari managed the latter, but the striker says it is an "honour" to be under his wing on the national stage.
"We all know the way we'll work will change," says the 21-year-old. "Scolari is like a father, he treats everyone in the best possible way.
"I have worked against him, but this is the first time we are on the same side. It's an honour."