Much of the university spin-offs (USOs) literature either focuses on the influence of parent universities or the external environments on enterprise performance in economies with one aspect almost always neglected, that is, the role of USOs' corporate governance. In this study, we examine the effects of USOs' corporate governance structure which includes equity structure, board size and organizational form, on enterprise performance in a Chinese context, as well as the moderating effect of human capital on the relationship between board size and enterprise performance. This study takes 150 enterprises in 42 universities in Hubei Province as samples in 2017 using the weighted least square (WLS) method. The research finds evidence of positive relationships between equity structure and enterprise performance, as well as between board size and enterprise performance. However, a positive effect is not found between organizational form and enterprise performance, which shows a prominent negative effect. Moreover, human capital which is partially positive, influences the relationship between board size and enterprise performance. Therefore, these findings add some potentially noteworthy dimensions to the USOs literature that are especially important to USOs' policy makers and other stakeholders.