Based on the perspective of planning behavior theory, starting from the trainable political skills, this study explores the impact mechanism of employees' political skills on promoting their active boundary spanning behavior through 234 research samples from 12 enterprises. The results show that employees' political skills have a significant positive impact on boundary spanning behavior; the boundary spanning efficacy plays a partial intermediary role between political skills and boundary spanning behavior; employee power distance negatively regulates the relationship between their political skills and boundary spanning efficacy, and negatively regulates the intermediary role of boundary spanning efficacy between political skills and boundary spanning behavior. The research results can enrich and expand the relevant research on political skills and boundary spanning behavior, and can provide insights on how to encourage more boundary spanning behavior in organizations.