The present study sought to investigate the associations between workplace bullying and personal burnout both directly and indirectly via work-life conflict. Furthermore, the moderating role of gender in these relations was examined. Traditional research on stress at work focuses on the role of dimensions related to job tasks, demands, and organizational support in influencing the risks for stress-related problems in employees. At the same time, other experiences at work may reduce employees’ well-being, such as workplace bullying and family life. Specifically, considering the detrimental role of work-life conflict, it is possible to hypothesize that it would exacerbate workplace bullying’s harmful effects on employees’ health. Moreover, since previous studies have reported mixed or inconsistent results when considering gender differences with the above-mentioned dimensions, it seems worth investigating the role of employee gender in representing (and response to) the bullying experiences. Building on these considerations, this work verifies whether: (1) work-life conflict mediates the relationship between workplace bullying and burnout; (2) gender moderates all the possible relationships among the constructs. Such hypotheses are verified on a sample of school principals, in light of their peculiar job role. Overall, our findings showed that: (1) Workplace bullying and burnout are associated, both with and without the perception of a concurring work-life conflict; (2) Gender does not moderate all the possible relationships among workplace bullying, work-life conflict and burnout. Overall, being female heightens the risk to perceive work-life conflict in general, as well as to be burnt out, when bullied, with and without the presence of work-life conflict; being male heightens the risk to perceive work-life conflict when bullied. Furthermore, the current findings suggest that family demands may influence school principals’ feelings of exhaustion regardless of gender. These findings confirm and expand previous literature, especially concerning a less studied occupation, namely school principals, shedding a new light on their work experiences. Furthermore, the present study offers interesting implications for trainings on principal’s skills and professional identity.