By applying the supplies-values (S-V) fit approach from the complementary person-environment (P-E) fit literature to the leader-employee perspective, and drawing upon social exchange theory, we examine how fulfillment of different work values is related to Leader-Member Exchange (LMX) and work outcomes. First, polynomial regression analyses combined with response surface analysis of data collected at two time points (N = 316) showed that LMX (Time 2) was higher the more the leader fulfills the employee's work values (Time 1). Second, LMX (Time 2) was higher when leader supplies (Time 1) and employee work values (Time 1) were both high than when both were low. Third, analyses of data from a sub-sample of matched leader-employee dyads (N = 140), showed that LMX (Time 2) played a mediating role on the relation between S-V fit (Time 1) and work outcomes (Time 2). Specifically, we found eight out of 10 relationships between S-V fit (Time 1) and leader-rated task performance and OCB (Time 2) to be fully mediated by LMX (Time 2). LMX (Time 2) partially mediated the relation between S-V fit (Time 1) and job satisfaction (Time 2) as only two out of five relationships were fully mediated.