Work stressors are related to poor psychological detachment (i.e., mentally "switching off") from work during nonwork time, which in turn is related to low levels of recovery and health. This article examines two general personality orientations, attachment avoidance and attachment anxiety, and one vocation-specific personality tendency, overcommitment, as buffers of the work stressors–psychological detachment relationship. Survey data were collected from a sample of Israeli employees (N = 210) and their significant others (N = 109) to avoid same-source bias of psychological detachment assessments. Analyses showed that attachment avoidance moderated the negative association between workload and psychological detachment (self-reported), but attachment anxiety did not moderate the associations of role conflict and role ambiguity with psychological detachment. Overcommitment was a full mediator between job stressors (workload and role conflict) and psychological detachment. This study demonstrates the importance of personality, especially vocational personality, in the work stressor–psychological detachment relationship.