This study assessed the associations of employee’s perceptions of family-supportive supervisor behaviors (FSSB) and their psychological distress across four occupational populations (n = 3778): Information technology; healthcare; military-connected Veterans; and National Guard service members. Data were gathered and analyzed from four larger archival datasets to compare differences in these relationships. Results revealed significant negative relationships between employee reports of FSSB and their psychological distress within occupations, as expected. Furthermore, results revealed significant differences across occupational populations for employee reports of both FSSB and psychological distress. Hierarchical moderated multiple regression analyses were conducted to examine the extent of these mean differences across groups. Results revealed significant differences among these four groups such that the military-connected Veteran employees demonstrated significantly stronger associations of FSSB, and psychological distress compared to the other three occupations of information technology, healthcare, and National Guard service members. These findings suggest the importance of FSSB to worker psychological health across a variety of occupational populations, specifically noting the importance and presence of FSSB for Veteran employees’ psychological distress in civilian workplaces. Practical implications include the need for training leaders on how to better support employees’ work and non-work lives, mental health, and well-being.