Manchester City midfielder Fernandinho, who has made just five appearances for his country, is the surprise addition to the squad, while Bayern Munich defender Rafinha, whose single cap for Brazil came in 2008, is also included.
David Luiz, Thiago Silva, Ramires, Oscar, Willian and Neymar have been included in the team as expected, but AC Milan's Robinho and Liverpool's Philippe Coutinho are two of the high-profile ommisions from Scolari's set-up.
The 65-year-old has so far only selected players based outside of Brazil, with the final spots to be filled nearer the beginning of next month.
"Fernandinho's been playing really well for Manchester [City], he's been attracting attention ... so here's his opportunity," Scolari explained at a news conference. "Rafinha's also been playing really well for Bayern. He's had experience of playing for the national team at other levels."
"This friendly against South Africa is a different situation. It's no use me taking 23 players, 18 or 19 is the most I'll be taking. I'm always watching the players who are in action. If there are surprises, it will be a normal thing," Scolari continued. "I always call the players who are in a best position. I'll test some more players and then define the final list.
"The ones who are training, working, I'm watching. We could have a surprise up until the last call-up."
Provisional squad in full:
Goalkeepers: Julio Cesar (QPR)
Defenders: Thiago Silva (Paris Saint-Germain), David Luiz (Chelsea), Dante (Bayern Munich), Daniel Alves (Barcelona), Rafinha (Bayern Munich), Marcelo (Real Madrid)
Midfielders: Luiz Gustavo (Wolfsburg), Fernandinho (Manchester City), Paulinho (Tottenham), Ramires, Oscar, Willian (all Chelsea)
Strikers: Neymar (Barcelona), Bernard (Shakhtar Donetsk), Hulk (Zenit)