The present investigation involved a systematic literature review to (1) identify associations between personality constructs and unprotected sex among people living with HIV/AIDS (PLWH); (2) assess patterns of direct versus indirect personality-risky sex associations; and (3) explore possible differences in personality-risky sex associations among PLWH versus non-infected populations. Among the 26 studies yielded through the systematic search, sensation seeking and sexual compulsivity were the constructs most frequently examined, with fewer studies investigating traditional personality typologies. Personality constructs that were more conceptually proximal to the sexual act, such as sexual compulsivity and sex-related sub-components of sensation seeking, showed relatively direct associations with unprotected sex, whereas more conceptually distal constructs such as generalized impulsivity demonstrated only weak or indirect associations. Associations were also frequently mediated by other risk factors, including perceived responsibility and substance use. These findings have implications for the development of interventions to reduce high risk sexual behavior among PLWH.