We examined the well-being of mothers and non-mothers reporting exclusive opposite-gender sexual partners (OG), same-gender sexual partners (SG), or both (BI) in a representative sample of 20,773 participants (11,034 women) 15-years-old or older from the population of Quebec province in Canada. Participants completed a self-administered questionnaire and SG and BI women (n = 179) were matched to a sample of OG women (n = 179) based on age, income, geographical area, and children (having at least one 18-year-old or younger biological or adopted child at home). We assessed social milieu variables, risk factors for health disorders, mental health, and quality of mothers' relationship with children. The findings indicated a sexual orientation main effect: Mothers and non-mothers in the SG and BI group, as compared to their OG controls, were significantly less likely to live in a couple relationship, had significantly lower levels of social support, higher prevalence of early negative life events, substance abuse, suicide ideation, and higher levels of psychological distress. There were no Sexual Orientation X Parenthood status effects. The results further indicated that sexual orientation did not account for unique variance in women's psychological distress beyond that afforded by their social milieu, health risk factors, and parenthood status. No significant differences were found for the quality of mothers' relationship with children. SG-BI and OG mothers with low levels of social integration were significantly more likely to report problems with children than parents with high levels of social integration. We need to understand how marginal sexualities and their associated social stigma, as risk indicators for mothers, interact with other factors to impact family life, parenting skills, and children's adjustment.