Most studies on citizenship behaviors centered on organizational citizenship behavior and its contributions to the organization performance. However, there also exists extra-role behaviors which is involuntary, as compared to the traditional Organizational Citizenship Behaviors. They are the compulsory citizenship behavior forced by the external stress in the workplace. It has become an important topic in the field of organizational behaviors. However, despite an increasing number of related studies, there is still little empirical research on this topic. Besides, the relationship between compulsory citizenship behaviors and work-family balance has not been explored. This study examines the responses of 198 knowledge staff in two of the Beijing high-tech enterprises. Using statistical method of Bootstrapping and path analysis, all the hypotheses were tested. The results indicate: employees’ compulsory citizenship behaviors are negatively related to their work-family balance; work stress mediates the relationships between compulsory citizenship behavior and work family balance; proactive personality moderates the effects of the compulsory citizenship behavior on employees’ work stress, work-family balance. These discoveries are not only useful for us to get more comprehensive and reasonable view of employees’ compulsory citizenship behaviors, but also provide valuable reference for managers. Organizations can effectively restrain compulsory citizenship behavior’s negative effects for the purpose of improving organization efficiency.