The current study investigated the interaction effect of perceived overqualification and LMX on employee emotional exhaustion, and examined the mediating role of work alienation from the perspective of relative deprivation theory. Using a sample of 297 employees in 12 companies collected in China, we found that perceived overqualification was more positively related to work alienation and emotional exhaustion when LMX was high than when LMX was low. The results of the mediated moderation analysis revealed that work alienation mediated the interaction of perceived overqualification and LMX on emotional exhaustion.