Italy's Manassero, the youngest winner on the tour, and Spain's Jimenez, the oldest winner, were confirmed on Tuesday for the tournament at Durban Country Club from Jan. 10-13.
India's Jeev Milkha Singh and former British Open champion Darren Clarke also have entered the third event on the 2013 Race to Dubai.
Manassero was 17 when he claimed the 2010 Castello Masters title. Jimenez won last month's Hong Kong Open at 48.
Ryder Cup winners Nicolas Colsaerts, Paul Casey, Peter Hanson, Paul Lawrie and Francesco Molinari already were confirmed for the Volvo Golf Champions.
The new European season begins with three successive events in South Africa, starting with this week's inaugural Nelson Mandela Championship.