The epidemiology of HIV in urban centers of the United States such as the District of Columbia (DC) is dynamic with rates of new HIV and AIDS diagnoses as well as risk factors elevated. Correlates of HIV among heterosexual women extend beyond traditional, individual risk factors to structural factors. The purpose of this study was to compare proportions of HIV and correlates of HIV among women participating in National HIV behavioral surveillance (NHBS) system in 2006–7 (NHBS Cycle 1) and 2010 (NHBS Cycle 2). Analysis of 677 female participants at elevated risk for HIV revealed high prevalence of individual-level HIV-associated risk factors (e.g., sexual behavior) and socio-structural associated risk factors (e.g., homelessness, incarceration, lack of health insurance). While a greater proportion of women were HIV-infected in Cycle 2, after controlling for the distribution of demographic characteristics to adjust for a change in eligibility criteria, the pooled sample did not reveal a significantly increased proportion of HIV-infected women in Cycle 2. Homelessness and condom use were associated with greater relative odds of HIV after adjustment for confounders, and non-injection drug use was associated with reduced odds. Findings inform our understanding of the continuing HIV epidemic in DC and support development of effective interventions to slow the epidemic among women in DC and similar urban centers.