This study empirically examines the relationship between family-friendly policies—introduced and implemented to support work-family balance among organizational members—and psychological dimensions of organizational effectiveness, including job satisfaction, organizational commitment, and organizational citizenship behavior. Furthermore, in order to identify the specific psychological mechanisms through which the effects of family-friendly policies are generated among organizational members, this study formulated and tested the hypothesis that the effects of family-friendly policies would be partially mediated by the "work-family conflict" and "work-family enrichment" experienced by these members. Therefore, this study is significant in that it simultaneously compares and examines the mediating effects of work-family conflict and work-family enrichment factors in testing the effectiveness of family-friendly policies. Based on a survey of 293 employees at Company H, which had been certified as a family-friendly enterprise, the results confirmed that family-friendly policies had a positive relationship not only with job attitudes related to formal tasks, such as job satisfaction and organizational commitment, but also with organizational citizenship behavior in non-task dimensions, including altruistic behavior and active participation. In addition to this direct effect of family-friendly policies, an indirect effect mediated through the enhancement of work-family enrichment was also confirmed. Specifically, work-to-family enrichment originating from the workplace partially mediated the effect of family-friendly policies on all effectiveness variables introduced in this study, and family-to-work enrichment originating from the family partially mediated the effect on organizational commitment and organizational citizenship behavior. However, work-family conflict did not exhibit such a mediating effect and instead emerged as a factor that directly and negatively affects job-related attitudes. The managerial implications suggested by these analytical results and directions for future research were discussed.