Based on the panel data of Chinese listed outward investment enterprises from 2013 to 2017, the internal mechanism and effect differences of female executives’ participation on enterprises’ outward investment speed and outward investment quality are investigated, and the moderating effects of internal and external factors such as institutional distance and comprehensive capital of executives on the above relationships are also examined. The results show that the participation of female executives inhibits the increase of outward foreign direct investment (OFDI) speed, but significantly contributes to the improvement of OFDI quality. Further analysis reveals that there are hierarchical differences in the effects of female executive participation on the outward investment of enterprises, the introduction of the institutional distance factor weakens the positive effect of female executive participation on the quality of the outward investment of enterprises, and the adjustment of enterprise executives’ comprehensive capital to the effect of female executives’ participation is not significant. The conclusion provides empirical evidence for the optimization of human resource allocation and strategic convergence of enterprises in the transition period.