Mlambo completed his much-speculated move to the Buccaneers on Monday, and attended his first training session with his new teammates on Tuesday.
The former Chippa United midfielder spent just 18 months at the Milpark-based outfit, where he helped the club win the MTN8 and Absa Premiership titles in his first season.
However, the 26-year-old fell out of favour after Gavin Hunt's side bagged the Telkom Knockout Cup in December last year, and was left out of their matchday squads for all their league fixtures since the defeat to Sundowns in November.
Mlambo has since moved on and reunited with a few familiar faces in the Bucs camp, who helped him deal with the frustrations he experienced over the last three weeks at Wits.
"There are a few faces in the team that I go back a long way with because of our collective past experiences," Mlambo told Pirates' website.
"Mpho Makola is special, he is more of a brother than a teammate for me. When things were bad and I didn’t train for three weeks because I was stopped from training with Wits, he was there for me in what was an extremely frustrating time for me.
"We chatted all the time and he always advised me and kept me believing that I am a quality player and that things will work out."
Mlambo added that Bucs assistant coach Rhulani Mokwena also provided some support prior to his transfer.
"Coach Rhulani was instrumental in keeping me motivated and ensuring that I continue to train hard during those three weeks when I was on my own," he added.
"We go way back, even before I turned professional. I started working with him before I left the reserve team of Mamelodi Sundowns to join Cape Town All Stars."