Among the main causes of absenteeism are health problems, emotional problems, and inadequate work-family policies (WFP). This paper analyses the impact of the existence and accessibility of WFP on work absenteeism, by considering the mediating role of the well-being, which includes emotional as well as physical or health problems, that is generated by these policies. We differentiate between the existence of the WFP and its accessibility, as the mere existence of the WFP in an organisation is not enough. Additionally, workers must be able to access these policies easily and without retaliation of any kind. The model includes the hierarchy and the gender as moderating variables. To test the proposed hypotheses, a structural equation model based on the partial least squares structural equation modelling (PLS-SEM) approach is applied to a sample of employees in the service sector in Spain. On the one hand, the findings show that the existence of WFP has no direct effect on absenteeism; however, accessibility to these policies does have a direct effect on absenteeism. On the other hand, both the existence and accessibility of WFP have positive direct effects on emotional well-being. In addition, emotional well-being is positively related to physical well-being which, in turn, promotes a reduction in absenteeism. Finally, significant differences in the relationship between the existence of WFP and emotional well-being confirm the special difficulty of female managers in reconciling family life and work life.