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Alcohol use is associated with risks for HIV/AIDS. The association between alcohol and sexual risk may be accounted for by sensation seeking personality. However, sensation seeking in relation to substance use and HIV risk has not been examined in Africa. In this study, 292 men and 219 women receiving sexually transmitted infection (STI) diagnostic and treatment services in Cape Town, South Africa, completed anonymous behavioral surveys. Structural modeling was used to test a model of alcohol use and sensation seeking in relation to sexual risk behaviors. Results showed that sensation seeking and alcohol use in sexual contexts were related to HIV risks, controlling for gender and marital status. The association between sensation seeking and HIV risk was partly accounted for by alcohol use in proximity to sex. In contrast to studies conducted in the United States, sensation seeking was not related to alcohol–sex outcome expectancies. These findings suggest that alcohol use is an important HIV transmission risk factor for many STI clinic patients and that interventions for individuals who are characterized as sensation seekers are urgently needed in South Africa.