Based on the quasi natural experimental scenario of implementing the pilot of Accountability Audit of Natural Resources (AANR for short), taking China’s cities as research samples, this paper studies the impact of AANR on the implementation ability of government’s environmental governance. The results show that AANR can effectively improve the implementation ability of local government’s environmental governance, including implementation progress and implementation quality. The heterogeneity test results show that the shorter the departure time of the chief officials, the more officials demand for environmental performance, and the more significant the policy effect of AANR. The mechanism test results show that AANR affects the local government by optimizing the official promotion evaluation mechanism and strengthening the environmental supervision behavior. The research conclusion provides supporting evidence for the policy effect of AANR during its pilot period. Meanwhile, this conclusion has a certain theoretical contribution to understanding the implementation dilemma of local government environmental governance and provides policy enlightenment for promoting local government to undertake entrusted environmental responsibility.