Work well-being has attracted much attention with the rise of positive psychology, which focuses on positive attitude and affect at workplace, and plays a positive role for organization outcomes, such as organization performance, organization citizenship behavior and so on. Previous research suggests that various forms of person-environment fit are helpful to improve employees’ well-being, for example, person-organization fit and person-job fit can enhance employees’ work well-being. However, those studies mainly focus on other types of fit, without elaborating the basic process between person-supervisor fit and work well-being, in other words, some questions should be answered on this topic, first of which is through what internal mechanism person-supervisor fit operates on work well-being, and the second is what is the boundary condition of person-supervisor fit and work well-being. To answer the questions, we intend to explore how person-supervisor fit affects work well-being and when their relationship is changed. First, we reviewed the existing literatures about person-supervisor fit and work well-being. Second, based on the social exchange theory, we developed a model to examine the mediating role of leader-member exchange between person-supervisor fit and work well-being, and the moderating role of political skill between person-supervisor fit and leader-member exchange. In the end, we testified the hypotheses by empirical data. Data were collected among 209 employees in China through two wave surveys to reduce the common method bias. Person-supervisor fit , leader-member exchange and political skill were evaluated at the first time, and work well-being was evaluated one month after the first time. Confirmatory factor analysis results indicated that all variables have high reliability and validity, and four-factor model were better than other models. Hierarchical regression was used for data analyses. The results showed that person-supervisor fit was positively related to employee work well-being(β=0.165, P<0.01), leader-member exchange fully mediated the relationship between the person-supervisor fit and work well-being, and political skill played a negative moderating role between person-supervisor fit and leader-member exchange. In conclusion, this research examined the mediating role of leader-member exchange between person-supervisor fit and work well-being, which unveiled the underlying mechanism of person-supervisor fit and work well-being. Meanwhile, we also examined the moderating of political skill between person-supervisor fit and leader-member exchange, which revealed the boundary condition of person-supervisor fit and work well-being. This research not only answered the question of how and when person-supervisor fit affects employee well-being, but also examined the scientificalness of the social exchange theory. Thus, the research has a great significance to enrich the theoretical research of work well-being. The study has implicated that organizations could enhance the fit between employees and their supervisor by selection, training, and so on. What’s more, supervisor can develop and strengthen the special interests of supervisor and subordinate to affect the cognition of person-supervisor fit. Then, organization should pay much attention to the role of leader-member exchange. Finally, remind employee should use political skill reasonably. At the end of the article, we point out the limitations and future research directions. Data were collected among 209 employees in China through two wave surveys to reduce the common method bias. Person-supervisor fit , leader-member exchange and political skill were evaluated at the first time, and work well-being was evaluated one month after the first time. Confirmatory factor analysis results indicate that all variables have high reliability and validity, and four-factor model were better than other models. Hierarchical regression was used for data analyses. The results showed that person-supervisor fit was positively related to employee work well-being(?=0.165,P<0.01), leader-member exchange fully mediated the relationship between the person-supervisor fit and work well-being, and political skill played a negative moderating role between person-supervisor fit and leader-member exchange. In conclusion, this research examined the mediating role of leader-member exchange between person-supervisor fit and work well-being, which unveiled the underlying mechanism of person-supervisor fit and work well-being. Meanwhile, we also examined the moderating of political skill between person-supervisor fit and leader-member exchange, which revealed the boundary condition of person-supervisor fit and work well-being. This research not only answered the question how and when person-supervisor fit affects employee well-being, but also examined the scientificalness of the social exchange theory. Thus, the research has a great significance to enrich the theoretical research of work well-being. The study has implicated that organizations could enhance the fit between employees and their supervisor by recruit, train, and so on. What’s more, supervisor can develop and strengthen the special interesting of supervisor and subordinate to affect the cognition of person-supervisor fit. Then, organization should pay much attention to the role of leader-member exchange. Finally, remind employee should use political skill reasonably. At the end of the article, we point out the limitations and future research directions.