With a shortage of resources and perfect institutions，it is difficult for new ventures to obtain valuable resources． More and more researches study how entrepreneurs employ their political skills to develop potential resources hidden in the interpersonal network． In China，entrepreneurs’political skills ( EPSs) play a key role in the process of resource acquisition． By the strategies of rationality or emotionality，the entrepreneurs with high political skills can not only obtain organizational resources，but also can rely on affective inter-action to invoke organizational capabilities in daily practice． Using the mixed method research，this study first establishes a theoretical model with the quantitative method，and then further extends the model with the qualitative method in everyday workplace． The findings suggest that EPSs，which is the component of social competence，have effects on resource acquisition process through their strategies of rationality or emotionality． In the role-relationship between the entrepreneurs and resource owners，the existing resources are obtained through the strategy of rationality when the relationship is weak，and the strategy of emotionality favors potential resources when the relationship is strong． In the renqing situation，the strategy of emotionality facilitates the invocation of personal network and potential resources．