The purpose of this study was to identify key psychosocial characteristics of HIV-infected women who exhibit different levels of both ART adherence and risk behaviors. We analyzed baseline data from 193 predominately African American HIV-infected women participating in a behavioral clinical trial. Women were categorized into high/low groups based on levels of adherence and risky behaviors. There was a significant interaction effect for internal motivation for adherence. Women at high risk for poor health and transmitting HIV (low adherence/high risk group) had the lowest levels of internal motivation and also reported more difficult life circumstances. Gender roles, caretaking and reliance on men for economic and other support may promote external versus internal motivation as well as riskier behaviors in this group. The highest levels of internal motivation were found in those with High Adherence/High Risk behaviors. This group was highly knowledgeable about HIV and had the lowest VL. Compared to others, this group seems to tolerate risky behaviors given their high level of adherence. Adherence and risk reduction behaviors are key to individual and public health. Motivation and risk compensation should be addressed when providing interventions to women living with HIV.