As more people are living long-term with HIV there are growing concerns about specific behaviors that can affect both personal and the public health. This study examined the relationship between antiretroviral therapy (ART) adherence and sexual risk behavior and their association with psychosocial and health factors among a diverse sample of 2,849 HIV-infected adults. Only 8.5% of the sample reported both non-adherence and sexual risk. Individuals were 46% more likely to report one of these risk outcomes when the other one was present and the presence of both outcomes was associated with an increased likelihood of having a detectable viral load. A simultaneous polytomous regression analysis revealed complex relationships among a range of psychosocial variables and the two primary behavioral risk outcomes. There is a need for targeted interventions and integration of mental health and substance use services into primary HIV care settings.