Studies on the impact of work-family dynamics on both parenting and children’s outcomes are scarce. The present study addressed this gap by exploring how parents’ negative (conflicting) and positive (enriching) experiencing of work and family roles related to children’s internalizing and externalizing problem behaviors through its association with the quality of parent-child relationships. A sample of 317 dual-earner couples with preschool children was used to conduct a dyadic analysis of both within- and cross-dyad influences of parents’ work-family experiences on child problem behaviors. Our results indicated that the way parents balance work and family is associated with their parent-child relationships, which in turn is differentially linked with their children’s behaviors. We found that mothers’ work-family conflict (WFC) contributed to children’s externalization difficulties through its detrimental associations with their own and with their partners’ parent-child relationship quality. By contrast, mothers’ work-family enrichment (WFE) was negatively linked to children’s externalization difficulties through its positive link with the mother-child relationship. Fathers’ experience of WFC was associated with both children’s internalization and externalization difficulties through its negative association with their own father-child relationship quality. In addition, fathers’ experience of WFE also linked to children’s externalization difficulties, but only indirectly, via its positive association with the quality of their relationship with the child. Further implications of these findings for advancing understanding of the impact of work-family dynamics on intrafamily relationships, as well as for individual and organizational interventions, are discussed.