Past research has primarily investigated the role of the negative side (family-to-work conflict; FWC) of the family-to-work interface in workplace safety outcomes and neglected the positive side (family-to-work enrichment; FWE). Moreover, the mechanism underlying the relation between the family-to-work interface and workplace safety has not been well studied. From the perspectives of the job demands-resources model as well as conservation of resources theory, this study endeavors to extend the current literature on workplace safety by evaluating the mediating roles of burnout, work engagement, and safety violations in the associations of FWC and FWE with workplace injuries. Two-wave longitudinal survey data were obtained from 233 Chinese employees in two high-risk industries (nursing and railways). The hypothesized longitudinal mediation model was analyzed with the structural equation modeling technique. It was revealed that the association of FWE with workplace injuries was mediated by work engagement and then safety violations. Burnout was found to mediate the association of FWC with workplace injuries. Safety violations were also found to mediate the association of FWC with workplace injuries. The present findings offer insights into the underlying mechanisms by which the family-to-work interface influences workplace injuries.