How to regulate employee conduct and engage them in high performance works actively and continuously has always been the important topic for organizations. Based on affective events theory and social exchange theory, a moderated mediating model was constructed with the affective commitment as mediator and the supervisor–subordinate exchange guanxi as moderator. Regression analyses and conditional indirect effects were tested by SPSS and PROCESS with 374 matched supervisor–subordinate pairs. The paper explores the moderated mechanism of supervisor-subordinate guanxi to the chain of “ambidextrous leadership–employee’s affective commitment–workplace deviance behavior.” The results showed that the affective commitment mediated the effect between ambidextrous leadership and employees’ workplace deviance behavior, and supervisor–subordinate exchange guanxi moderated the relationship between ambidextrous leadership and employees’ workplace deviance behavior but also moderated the mediating effect of affective commitment. The results have significances to improve human resource management practices and reduce the workplace deviance behavior of employees.