Leader hypocrisy refers to perceptions of a leader's word–deed misalignment. This study explores the mechanisms underlying the relationship between leader hypocrisy and psychological withdrawal as an indicator of nonprofit employees' disengagement from work. We propose that leader hypocrisy indirectly relates to employees' psychological withdrawal behaviors by influencing the quality of their relationships (leader-member exchange [LMX]) with their leaders. Within this mechanism, we differentiate two routes that can lead followers' perceptions of leader hypocrisy to LMX: trust in the leader and negative emotions. Data were gathered from 182 employees working in a variety of nonprofit organizations (NPOs) in two waves. The findings support the indirect effect of leader hypocrisy on psychological withdrawal through trust in the leader and LMX. However, the mediating effect of negative emotions was not supported as the direct path from negative emotions to LMX was not significant. By adding a direct path, the alternative model demonstrated that when employees perceive their leader as a hypocrite, negative emotions can directly create psychological withdrawal rather than influencing withdrawal through impairing relationship quality perceptions.