Different from prior literature in the financial and legal domains which focused on the impact of legal provisions on economic behaviors, our study delves into the effects of law enforcement efficacy within a unified legal framework, which exhibits variations across provincial levels within a country. Specifically, we explore how these enforcement qualities impact risk-taking tendencies and the likelihood of successful exits following venture capital firm (VC) investments. We used a sample of 45,582 rounds of VCs investments in Mainland China and then found that law enforcement quality is of positive correlation with VCs risk-taking and probability of successful exit after investment, i.e., the difference in law enforcement quality in provinces under the same legal framework can affect VCs’ risk-taking and probability of successful exit after investment. Specifically, provinces with low law enforcement quality where VCs have a lower risk-taking level, are less inclined to invest in early-stage and high-tech projects and have a lower probability of undertaking IPOs for their investments. In contrast, in the provinces with higher law enforcement quality, VCs have higher risk-takin and probability of successful exit after investment. Furthermore, enforcement quality also has an impact on the source and investment modes of VCs. Lower law enforcement quality negatively impacts international VCs more than local VCs and negatively impacts modes of syndication more than independent investment. Therefore, according to the findings of this paper, Mainland China should improve the law enforcement quality in provincial regions when improving its business environment.