Little work has examined relationship dissolution or divorce in adoptive parents or same-sex parent couples. The current study examined predictors of relationship dissolution across the first 5 years of parenthood among a sample of heterosexual, lesbian, and gay male adoptive couples. Of the 190 couples in the study, 15 (7.9%) dissolved their relationships during the first 5 years of adoptive parenthood. Specifically, 7 of 57 lesbian couples (12.3%), 1 of 49 gay male couples (2.0%), and 7 of 84 heterosexual couples (8.3%) dissolved their unions. Results of our logistic regression analysis revealed that the odds of relationship dissolution were significantly higher for (a) couples who adopted a non-infant (i.e., older) child); (b) participants who reported feeling less prepared for the adoption, three months post-adoptive placement; and (c) couples in which both partners reported very low, or very high, pre-adoption levels of relationship maintenance behaviors. Findings have implications for adoption professionals seeking to support same-sex and heterosexual prospective adopters, as well as societal debates and policy regarding same-sex relationships and parenting.