The 25-year-old arrives from Kaizer Chiefs, having previously played for Rostov in Russia, as well as Mamelodi Sundowns. Xulu has signed a three year deal.
Also confirmed as joining the Team of Choice are defenders Rushine De Reuck and Motsie Matima, midfielders Mxolisi Kunene and Liam Youlley, and goalkeeper Richard Ofori and Jethren Barr.
Maritzburg start their season on August 13 when they play Sundowns in an MTN8 match in Pretoria.
Head coach Fadlu Davids on Xulu's arrival:
"Siyanda Xulu is a huge signing for us and will give us the necessary experience in defence and of course the quality in the defensive department, especially after losing the experience of Themba Shabalala.
"It really shows the great intent from the club as the chairman has spoken about the top five. This shows real intention in bringing players of Siyanda's calibre and magnitude to the club. With him only being 25 years of age we feel he'll be at the club for years to come."
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