Using appraisal theories of emotions as the theoretical basis, we delineate how perceived overqualification relates to work withdrawal, employee silence, and pro-job unethical behavior through the mediating effects of discrete emotions (i.e., shame and anger). We suggest that perceived overqualification is positively associated with shame and ultimately work withdrawal and employee silence, and it has a positive effect on pro-job unethical behavior through the mediating role of anger as well as the serial mediating effect of shame and anger. Data from a three-wave, time-lagged survey of 225 full-time employees in China, provides support for our theoretical model and hypotheses. Taken together, our results suggest that discrete emotional states can help to interpret how and why overqualified employees exhibit distinct action tendencies. We discuss the theoretical and practical implications of our findings.