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Increasingly, new HIV infections among people who use drugs are attributed to sexual risk behavior. However, HIV prevention research targeting persons with opioid dependence continues to focus on drug injection practices. Moreover, despite the rising prevalence of prescription opioid dependence in the United States, little is known about HIV risk in this population.This study examined the prevalence of sexual risk behavior among patients with opioid dependence who primarily use prescription opioids for non-medical purposes. As part of a multi-site clinical trial, participants (N = 653) completed a baseline assessment that included the Risk Behavior Survey.In the past month, 74% were sexually active. Of these, most had opposite sex partners (97.3%) and vaginal intercourse (97.1%); anal intercourse was uncommon (3.1%). The majority reported unprotected intercourse (76.5%), but few had multiple partners (11.3%). Unprotected intercourse was associated with history of other substance dependence (adjusted odds ratio [AOR] = 1.73), and having multiple partners was associated with concurrent cocaine use (AOR = 2.54). Injection drug use in the past month was rare (2.5%).While the majority of sexually active participants engaged in unprotected intercourse, the proportion with multiple sex partners was low relative to other samples of persons who use illicit drugs. Among persons with non-medical prescription opioid dependence, those who concurrently use other substances may be at elevated risk for HIV infection. Comprehensive assessment of substance abuse history among individuals dependent upon prescription opioids is critical for identifying patients who may require additional clinical interventions to reduce HIV sexual risk behavior.