Condom use has increased significantly over the past decade among all adult age groups in South Africa, and it is widely believed to have played a major role in the recent significant decline in HIV incidence in the country, especially among young people. This study investigated the demographic, behavioural and psychosocial correlates of condom use at last sex among a national random probability sample of sexually experienced respondents aged 15 years and older (n = 7817, 42.9% males and 57.1% females) using data from the 2008 South African national HIV population-based household survey. Multivariate logistic regression analyses revealed that for both sexes, being aged 15–24 years and 25–49 years old, Black African, never married and unemployed were significantly associated with condom use at last sex. In addition, for males, condom use was associated with having had two or more sexual partners, whereas for females it was associated with living in urban formal, urban informal and rural informal areas, and having been in a current relationship for less than a year. Based on these findings, it was concluded that there is a need to further promote condom use especially among the subgroups of people with lower rates of condom use in order to reduce their risk of HIV infection.