It is not uncommon for employees to engage in deviant workplace behavior. Several studies have been conducted on its antecedent variables and negative effects on the organization and its members. However, the effects on employees’ emotions and behavior have been ignored. According to the affective events theory and framework of organizational shame, this study examined how deviant workplace behavior affects employee performance, explored how organizational shame mediates, and investigated the role of perceived organizational support moderators. This study was completed by 435 Chinese employees in total. The results showed the following. (1) Deviant workplace behavior significantly positively predicted organizational shame and negatively predicted job performance. Organizational shame positively predicted job performance. (2) Organizational shame mediated the relationship between deviant workplace behavior and job performance, and there were gender differences in this mediating role. (3) Perceived organizational support weakened the negative effect of deviant workplace behavior on job performance. As a result, this study proves the applicability of the framework of organizational shame in a Chinese context and provides support for the affective events theory, from the perspective of actors. Furthermore, this study offers insight into how to ameliorate the negative effects of deviant workplace behavior.