The purpose of this 16-year prospective follow-up study was to investigate the association between parental divorce in childhood and intimate relationship quality in adulthood. The mediating role of psychosocial resources (parent-child relationships at 16 years, self-esteem and social support at 32 years) in this association was also studied. All 16 year olds of one Finnish city completed questionnaires at school and were followed up by postal questionnaires at 32 years of age (n = 1,471). Results showed that women and men from divorced families were more often divorced or separated at the age of 32 years than those from nondivorced families. However, parental divorce was associated with poorer intimate relationship quality only among women. Women from divorced families also had poorer relationships with their father and mother in adolescence, and they had lower self-esteem and satisfaction with social support in adulthood than women from intact families. No such associations were found among men. The impact of parental divorce on intimate relationship quality among women was partially mediated by mother-daughter relationship, self-esteem, and satisfaction with social support. The mediating role of mother-daughter relationship was not direct, however, but was mediated via self-esteem and satisfaction with social support. Our findings indicate that parental divorce affects daughters more than sons. In the context of parental divorce, the mother-daughter relationship in adolescence is important for the development of later psychosocial resources and, via them, for intimate relationship quality.