This study constructs a digital economy (DE) index and explores its impact on environmental quality by utilizing data from China’s 287 prefecture-level cities from 2013 to 2019. Unlike past studies, this research examines the indirect effect of DE on environmental pollution through the channels of industrial structure and educational investment. Further, it also analyzes the moderating role of economic globalization and green technology innovation in the nexus between DE and environmental quality. The empirical results indicate that DE significantly and positively enhances environmental quality by mitigating environmental pollution. This outcome remained stable after a series of empirical analyses and stability checks. Secondly, DE positively affects ecological and environmental quality by improving education levels and upgrading industrial structures. Thirdly, green technological innovation and economic globalization positively and significantly moderate the effect of DE development on ecological and environmental quality. Fourthly, associations between the development of DE and environmental quality are heterogeneous in terms of regions and markets, among which the most significant impact exists in the eastern area and the area with higher marketization. Based on the empirical findings, this paper provides comprehensive recommendations for promoting the DE and advancing China’s environmental quality. Based on the results, important policy implications are suggested.