Based on the work-family enrichment theory, this study analyzes the contribution of work-family and family-work enrichment to explain the military’s well-being during a peacekeeping mission. The data used were collected in a sample of 306 Brazilian soldiers, who were married and/or had children, during the phase named “employment of troops” (i.e., when peacekeepers had been in the Haitian territory and, as a result, away from their families, for between three to five months). Data analysis was performed using the Structural Equations Model. It was observed that the military’s perception of their spouses’ support for their participation during the mission had a positive relationship with both family-to-work enrichment and work-to-family enrichment, and the work-to-family enrichment mediated the relationship between the perception of the spouses’ support and the military’s health perception and general satisfaction with life. Theoretical and practical implications were discussed and limitations and suggestions for future research were presented.