The 27-year-old centre-back is joining the Soweto giants as a free agent after parting ways with Stellenbosch after the 2025/26 season concluded.
He has made 142 appearances in the top-flight following a short spell at Maritzburg United before moving to the Western Cape to play for Stellenbosch in 2023.
"Kaizer Chiefs are delighted to announce the arrival of Thabo Moloisane for the upcoming season," read the statement on the club website and social media.
"Importantly, he brings valuable experience of African competition, having featured in the Confederation Cup. His continental pedigree will be key for Amakhosi as the team returns to CAF competition for another season."
Moloisane also has two Bafana Bafana caps to his name under coach Hugo Broos and will be looking to push into the side following the conclusion of the FIFA World Cup 2026.