<p>Drawing on the conservation of resource theory, the study presents a theoretical model to examine how and when servant leadership motivates employees’ taking charge behavior. The study collected the employee-leader dyad data in three waves, each with an interval of two weeks. The statistical analysis of the 315 three-wave, multi-source data reveals that psychological availability plays a mediating role in the transmitting process from servant leadership to followers’ taking charge behavior. Political skill moderates not only the relationship between psychological availability and taking charge but also the indirect effect of servant leadership on taking charge via psychological availability, such that the relationship and the mediating mechanism are stronger when followers have a high level of political skill as opposed to a low level. The study provides a new perspective of the underlying mechanisms for leaders to fuel the taking charge behavior. At last, we discuss the theoretical and practical implications as well as future research directions of the findings.</p>