The digital economy plays a dual role in the process of global carbon emissions decoupling; for this reason, its overall impact direction and mechanism are worth discussing. This paper attempts to answer the question of the role of the digital economy, based on a review of the existing literature. By constructing a panel smooth transition regression (PSTR) model, this paper empirically tests the effect of the digital economy on carbon emissions decoupling, based on panel data from 30 provinces in China from 2010 to 2019. In order to study the impact mechanism of the digital economy on carbon emissions decoupling, the mediating effect of industrial structure optimization is analyzed through a mediating effect model; the moderating effect is also explored by analyzing the network centrality characteristics of the digital economy. The core-periphery analysis method is adopted to group the samples to test the impact heterogeneity of the digital economy on carbon emissions decoupling. Based on this empirical analysis, the following conclusions are drawn. First, the digital economy has a promoting effect on carbon emissions decoupling, but this effect gradually weakens with the development of the digital economy. Second, the digital economy can promote carbon emissions decoupling through industrial structure optimization, and network centrality has a positive moderating effect on this mechanism. Third, heterogeneity exists in the promoting effect of the digital economy on carbon emissions decoupling, which is reflected in the different intensities of the promotion effect between the core nodes and the peripheral nodes in the network; the attenuation range of the promotion effect is also different when the regime switches.