Diplomatic relations between Italy and South Africa go as far back as 1929. Since then 25 Heads of Mission have led the Embassy:
• Natale Labia, Special Envoy and Minister Plenipotentiary with Letters of Credence (L.C.), 31 October 1929
• Gabriele Chiaramonte Bordonaro, Special Envoy and Minister Plenipotentiary, 8 June 1936
• Giuseppe Cosmelli, Special Envoy and Minister Plenipotentiary, 20 October 1939
• Ubaldo Rochira, Political Representative, 18 March 1946
• Pasquale Jannelli, Special Envoy and Minister Plenipotentiary, 9 October 1947
• Cristoforo Fracassi Ratti Mentone di Torre Rossano Special Envoy and Minister Plenipotentiary, 2 January 1951
• Carlo Fecia di Cossano, Ambassador with L. C., 12 September 1953
• Francesco Sily di Sant’Andrea D’Ussita, Ambassador with L. C., 26 January 1956
• Renzo Carrobio di Carrobio, Ambassador with L. C., 29 January 1959
• Augusto Assettati, Ambassador with L. C., 24 July 1962
• Alberto Paveri Fontana di Fontana Pradosa, Ambassador with L. C., 4 January 1967
• Alberto Paveri Fontana di Fontana Pradosa, Ambassador, 1 August 1969
• Aldo Pierantoni, Ambassador with L. C., 24 January 1971
• Giuseppe Meschinelli, Ambassador with L. C., 20 September 1975
• Giulio Cesare Di Lorenzo, Ambassador with L. C., 7 March 1979
• Giacomo Ivancich Biaggini, Ambassador with L. C., 1 February 1982
• Mario Piersigilli, Ambassador with L. C., 11 December 1987
• Bruno Cabras, Ambassador with L. C., 21 December 1993
• Renato Volpini, Ambassador with L. C., 7 February 1998
• Valerio Augusto Astraldi, Ambassador with L. C., 9 April 2002
• Alessandro Cevese, Ambassador with L.C., 3 luglio 2006
• Elio Menzione, Ambassador with L.C., 3 settembre 2008
• Vincenzo Schioppa, Ambassador with L.C., 24 novembre 2011
• Pietro Giovanni Donnici, Ambassador with L.C., 8 December 2015
• Paolo Cuculi, Ambassador with L.C., 15 April 2019