This study examined associations between warzone exposures to combat with postdeployment relationship and family functioning in 134 women who deployed to the conflicts in Afghanistan and Iraq. Survey invitations were sent by mail to 600 randomly selected women who experienced recent military deployments and were residing in New England. The web-based survey included measures of combat exposure, posttraumatic stress disorder (PTSD) symptoms, alcohol misuse, postdeployment stress exposure, family functioning, intimate relationship satisfaction, and parenting. Multivariate linear regression with bootstrapping estimates of indirect effects was used to examine whether PTSD symptoms and alcohol misuse accounted for associations between women's combat exposure and their postdeployment relationship and family functioning. Results indicated that women's PTSD symptoms had a direct and negative effect on postdeployment family functioning and on intimate relationship satisfaction. There was no direct association between combat exposure or alcohol misuse with any of the family or relationship functioning variables, however, the indirect association from combat to postdeployment family functioning (b = -.13, SE = 0.07, 95% confidence interval [CI]: -33, -.03) and intimate relationship satisfaction (b = -.25, SE = 0.18, 95% CI: -.79, -.001) was significant and negative through its association with PTSD symptoms. Parenting satisfaction was significantly and negatively associated with postdeployment stress only. This study is among the first to characterize the impact of deployment experiences on women veterans' relationship and family functioning. Findings suggest that women veterans who have been exposed to combat and who have higher levels of PTSD symptoms may benefit from relationship and family focused services after deployment.