In the context of carbon neutrality, the development of new digital infrastructure (NDI) and the improvement of digital capabilities are essential, in order to speed up the transformation of the energy structure. Based on the balanced panel data of 30 provinces in China from 2008 to 2019, we empirically analyzed the impact of NDI on the structural transformation of energy in China and its mechanisms of action. The results demonstrated that (1) NDI had a positive impact on China’s energy transition, and the empirical results were robust. (2) The mediating effect showed that NDI had a positive impact on the transformation of energy structure, through improving green total factor productivity and green finance. (3) The heterogeneity analysis indicated that NDI made a more significant contribution to the transformation of the energy structure in regions with lower pollution levels and in those with energy cooperation policies. This study provides a policy reference for Chinese energy transition from the perspective of the digital economy.