The rapid development of the new generation of digital technology and the increasing importance of the digital economy have brought new opportunities for China’s development and provided new ideas for the optimization of industrial structure as well as the improvement of industrial efficiency. In this paper, under the perspective of political economy, the evaluation index system of the comprehensive development level of the digital economy is constructed with the panel data of 30 Chinese provinces and municipalities from 2014 to 2023 as a sample, and the entropy weighting method is used to calculate the index of development. The rationalization and advanced upgrading of the industrial structure of the 30 provincial and municipal cities is studied by combining the Tel index and the added value of the tertiary/secondary industry. On this basis, the structural equation model was used to explore the role of the “digital economy” on “industrial structure upgrading”. The results of the study are as follows: the development level of China’s digital economy shows a stable growth trend from 2014 to 2023, with its average value increasing by 185.32%, and the average values of the advanced and rationalized levels of China’s industrial structure increasing and decreasing by 4.47% and 47.90%, respectively. The direct effect of the level of development on the improvement of industrial structure (i.e., Path 1) is significant, and the standardized path coefficient between the two is 0.162. The results of the study emphasize the need to comprehensively improve the level of development and to build an intermediary bridge between the digital economy and industrial structure upgrading by taking human capital, scientific and technological innovation, and consumption upgrading as important tools.