The digital economy and ecological environment are two major issues related to high-quality economic development. Scholars have not yet reached a unified conclusion about the link between the digital economy and pollution emissions, and the impact mechanism of the former on the latter needs further study. Using data from 278 Chinese cities from 2010 to 2019, this research employs coupling coordination analysis, fixed effect analysis and mediation analysis to examine the heterogeneous impact mechanisms of the expansion of the digital economy on urban pollution reduction from many angles. It discovers that, first, the growth of the digital economy has decreased the discharge of urban pollutants overall. Second, the impact mechanisms of the digital economy are heterogeneous. From a regional perspective, industrial structure supererogation plays an intermediary role in the relationship between digital economy development and pollution reduction in the eastern and central regions, but the mediating effect is not significant in the western and northeastern regions. In terms of the city development level, industrial structure supererogation has significantly mediated the relationship between the growth of the digital economy and the reduction of pollution in first- and second-tier cities, but this mediating effect is not significant in third-tier and other cities. Third, the above conclusions are still valid after the robustness test is carried out using instrumental variable estimation, replacement of the estimation method, and replacement of explanatory variables. This study is a useful contribution to research on the effects of the digital economy and the factors influencing pollution reduction. The results advance the study of the digital economy and also have practical implications for improving China’s ecological environment and fostering high-quality economic growth. Finally, we provide policy suggestions for the coordinated promotion of the digital economy’s development, industrial structure supererogation and environmental pollution reduction.