Under the support of Multi-Regional Input–Output (MRIO) analysis, this study constructs the Embodied Carbon Emission Transfer Network (ECETN) using the input–output tables of 42 sectors in 31 provinces of China in 2012, 2015, and 2017 and applies a series of complex network measurement indicators and analysis methods to describe its evolution features. The results show that the embodied carbon emission transfers between provinces generally narrow over time. With its high clustering coefficient and short average path length, ECETN has small-world characteristics and behaves sensitively, and changes in individual provinces can quickly spread and affect the entire system. In addition, the clustering effect and the spatial spillover structural properties of ECETN are explored based on the block model analysis. Finally, Quadratic Assignment Procedure (QAP) is used to analyze and quantify the contribution of provincial structural roles to ECETN, and it is found that spatial adjacency and differences in strength-in, strength-out, and betweenness centrality have significant positive effects, while differences in eigenvector centrality, clustering coefficient have significant negative effects. The restructuring of domestic trade can help achieve national emission reduction. These findings can provide more insights for the government to formulate future development directions and policies to reduce emissions further.