Drawing upon charismatic leadership and intrinsic motivation theory, we developed a theoretical model to examine the impact mechanism of charismatic leadership on employees’ tacit knowledge sharing intention in a temporary Enterprise Systems learning team. We conducted a survey-based field study to examine the theoretical model and hypotheses. A total of 153 questionnaires were distributed to ERP users of more than 20 subsidiaries of Beidahuang Group in China and 117 valid questionnaires were returned. Results from structural equation modelling analysis suggest that leader charisma has strong influence on psychological safety climate, which in turn has positive impact on individual’s intrinsic motivation and their tacit knowledge sharing intention. Our results unpack the impact mechanism of leader charisma on individual’s knowledge sharing behaviors, and provide guidelines for the team leader to exhibit appropriate leadership traits in order to promote a psychological safety climate and facilitate an effective knowledge sharing of Enterprise Systems.