This study examined how and when compulsory citizenship behaviors (CCB) lead to employees’ workplace deviant behavior (WDB) through psychological entitlement. In addition, this study integrates moral licensing and equity demand perspectives to further understand the psychological entitlement raising process. More specifically, this study verifies the moderating role of leader-member exchange (LMX) on the relationship between CCB and WDB and see if the strong supervisor-subordinate relationship facilitates CCB-workers to increase their entitlement and enhance their willingness to engage in WDB. Based on a sample of 299 elementary school teachers, the results provided supports for the hypotheses. This study found that CCB was directly positive related to WDB. Psychological entitlement was been verified the mediator role of the relationship between CCB and WDB. Moreover, the results also indicated that LMX moderated the mediating effect of psychological entitlement on the relationship between CCB and WDB such that the effect is stronger when LMX is high than when it is low. The effect of CCB on WDB found in this research supports the anticipation that CCB may bring about WDB. Furthermore, by confirming the mediating role of psychological entitlement in the linkage between CCB and WDB, such a finding substantially widens the scope of subordinate behavioral outcomes caused by CCB to include an important but neglected aspect of psychological mechanism, and thus is helpful for us to gain a more complete picture of the negative consequences of CCB. By applying moral licensing theory and focusing on a negative psychological configuration, this research also highlights the self-value inflation and vindictive mentality for explaining the transition process of CCB to WDB. By empirically testing LMX as one moderated mediating mechanism that underlies the influence of CCB on WDB, this research establishes an important theoretical perspective for explaining why high LMX employees are more likely to exhibit WDB, thereby contributing to understanding the “black box” of the transforming processes from CCB to WDB.