The coupling coordination development of rural revitalization and rural e-commerce is of great significance in promoting the economic growth of rural areas. Based on the observational data of 14 prefectural-level cities in Hunan Province from 2013 to 2021, this study analyzes the spatio-temporal evolution characteristics and driving factors of the coupling coordination development of rural revitalization and rural e-commerce in Hunan Province by adopting the methods of the coupling coordination model and spatial econometric model. The findings indicate that (1) the coupling coordination degree between rural revitalization and rural e-commerce has gradually increased, showing a transition path from dissonance to coordination; (2) there are regional differences in the coupling coordination degree between rural revitalization and rural e-commerce, with the overall difference showing a fluctuating narrowing trend, and the intra-regional difference is the principal cause for the overall difference; (3) the coupling coordination degree shows spatial clustering characteristics, with high–high clustering areas mainly concentrated in the eastern part of Hunan Province and low–low clustering areas concentrated in the western part of Hunan Province; and (4) there is a notable driving effect of infrastructure development, digitalization level, human capital, and regional consumption level on the coupling coordination of rural revitalization and rural e-commerce. Above all, this study provides effective recommendations for promoting the coordinated development of rural revitalization and rural e-commerce.