Brokerage has been not only acknowledged as a critical social network concept but also a pervasive organizational phenomenon. Whereas prior research has documented multiple advantages of brokerage, a predominant point suggests that brokerage does not foster trust and even undermine it given the specific positions and related control benefits. In this paper, we challenge this point and identify a specific type of brokerage, multiplex brokerage, the brokerage in multiplex networks, that could promote trust. We contend that individuals’ multiplex brokerage can enhance team members’ trust, which ultimately promotes their leadership emergence. Further, we propose that gender plays a moderating role in the aforementioned relationships. By analyzing the whole network data from 91teams and 604 employees, we found that team members’ cognitive trust mediates the relationship between multiplex brokerage and leadership emergence, and the indirect effect is stronger when the focal person is male rather than female. However, the mediating role of team members’ affective trust is not supported.