Although prior studies have shown that sensation seeking and impulsive decision-making are related to sexual risk-taking, it is still unclear whether these personality traits operate independently or synergistically. The purpose of this study was to elucidate the joint contribution of these personality traits to HIV and sexually transmitted disease (STD) risk behaviors using data from a large sample of sexually active young adults (N = 2,386). Regression modeling indicated that both sensation seeking and impulsive decision-making were consistently associated with sexual risk behaviors across 11 risk-related outcomes. Results further indicated that sensation seeking and impulsive decision-making operated synergistically with respect to the outcome variables of sex acts using drugs, acts with a partner using alcohol, and acts with a partner using drugs. In contrast to this, sensation seeking and impulsive decision-making operated independently with respect to the other sexual risk outcomes. Theoretical implications, as well as implications for HIV/STD prevention among high sensation seekers and impulsive decision-makers, are discussed.