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Recent research has suggested that trait impulsivity may predict sexual risk behavior. Few studies have examined this association directly in substance users at risk for HIV transmission. Participants were 330 primarily heroin and/or cocaine users who underwent a structured interview regarding their drug use, sexual behaviors, and impulsivity. Results from an iteratively reweighted least squares regression analysis indicate that impulsivity remained a statistically significant predictor of sexual risk after adjusting for the effects of demographic variables and substance use frequency (b = .179, p < .01). Frequency of cocaine use (b = .186, p < .01) was also significantly associated with sexual risk. These findings suggest that trait impulsivity may be an independent risk factor for sexual risk behavior among substance users, thus identifying potential targets for future interventions.