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The 32-year-old defender featured in 10 games for Jomo Cosmos in 1998 in his only Premier Soccer League action before moving to the Netherlands, and later Belgium and England.
"I've only played about 10 games in the PSL, and will need to adjust," Mokoena said on Friday.
"SA football is quick, but with my experience, thinking quicker will probably help me."
Mokoena was one of the high profile signings for ambitious Wits, who aim for a top five finish this campaign.
The club also recently signed Tinashe Nengomasha, Thomas Sweswe, both from Kaizer Chiefs, and Matty Pattison from Santos.
They are all expected to turn out for Wits in the pre-season Gauteng Cup in Atteridgeville on Saturday where they face SuperSport United in the first match.
Mokoena may partner another former Bafana skipper, Mbulelo Mabizela, in central defence, though Mabizela's fitness is a concern.
Kaizer Chiefs and Moroka Swallows are the other two teams participating in the tournament.
"It will be great rubbing shoulders with some of the guys I played with in the national team," Mokoena said.
"I know all the players who signed for Wits want to win and have a vision for the club."
Mokoena said he chose Wits over offers from China and Qatar, after leaving financially strangled English side Portsmouth, last season.
Many European-based players have returned to play locally, with Benni McCarthy coming back at the start of last season.
"We are not coming back because we failed overseas," said Mokoena.
"The PSL has improved, I had offers to finish off my career elsewhere."
While Mokoena said he has not retired from international football, he refused to speak on his relationship with former coach Pitso Mosimane.
Mosimane stripped him of the captaincy before being dropped from the team last year.
"I don't want to speak about Pitso," he said.
"But I have not retired from international football, but I'll first have to prove myself at Wits.
"I have not worked with (new Bafana coach) Gordon Igesund, but he has won trophies and can hopefully get the best of the team."
Meanwhile, Wits have bolstered their technical team with Andre Arendse, who started duty earlier this week.
The side's assistant coach Eric Tinkler will also sit on the bench on the weekend until the work permit of their new Spaniard coach Antonio Habas is in place.
