<h3>Background</h3> Over the past decade, HIV prevalence in Zimbabwe has significantly declined, with recent research attributing this decline to wide-spread behaviour change such as reductions in extramarital sexual partnerships. Despite these reductions in risky sexual Behaviours, infections could still be transmitted from one marital union to another as divorced or widowed HIV-positive persons remarry. <h3>Methods</h3> Using information collected through face-to-face interviews in 2003–2005 AND 2006–2008, we compared HIV prevalence and basic demographics among women and their spouses (married, or in a long-term or cohabiting relationship for >12 months) in Manicaland, Zimbabwe. We used logistic regression to assess differences in marital history and basic demographics between HIV seronegative concordant couples, HIV serodiscordant couples and HIV seropositive concordant couples. <h3>Results</h3> In nearly one-third of the 2836 (27.8%) of marital unions interviewed, at least one member was infected with HIV (n=787); both members were HIV positive in 372 couples (13%). Of the 415 serodiscordant couples, 157 (5.5%) were serodiscordant female positive. Overall, compared to those in seronegative concordant (NC) partnerships, women in female-positive discordant (FP) or seropositive concordant (PC) partnerships were older (25–34 years vs 15–24; OR 1.7, 95% CI 1.17 to 2.47; OR 3.35, 2.52 to 4.45, respectively), more likely to been divorced (FP OR 4.19, 2.83 to 6.20; PC OR 4.12, 3.10 to 5.48), and more likely to have been widowed (FP OR 7.83, 3.65 to 16.76; PC OR 7.86, 4.30 to 14.36). Similar but weaker trends in divorce/widowhood were observed among men in male-positive discordant relationships compared to men in SN relationships. Women in FP and PC partnerships both were nearly three times as likely to report >1 lifetime sex partners than women in SN partnerships (FP OR 2.82, 2.02 to 3.92; PC OR 2.86, 2.27 to 3.59); mean lifetime sex partners reported by women in FP and PC partnerships was similar (FP: 2.11 lifetime partners; PC 2.06). <h3>Conclusions</h3> HIV prevalence is high among persons in long-term, stable partnerships, and strongly associated with one or both partners reporting a history of divorce or being widowed. In particular, widowed and divorced women may play an important role in ongoing HIV transmission dynamics. VCT services and other interventions that target couples should be promoted among divorced and widowed individuals.