Based on the estimation of carbon emissions (CE) from the power sector throughout China’s 30 administrative regions in the period of 2003 to 2013, this study investigated the space-time evolution characteristic and its determinants using spatial autocorrelation test and the spatial Durbin model (SDM). The main results are as follows: (1) The CE from power sector increased from 1.58 billion tons to 3.88 billion tons, with an average annual growth rate of 9.54%, while obvious imbalance existed among different regions. (2) According to spatial analysis, the global Moran’s I values of CE from the power sector are significantly positive during the sample period, meaning that the CE has an obvious clustering effect. The local spatial autocorrelation index confirms the imbalance of spatial distribution of the power sector’s CE. (3) Results of the spatial Durbin model show that the urbanization rate, per capita GDP, and fee-based environmental regulations have a spatial spillover effect. Based on the above findings, several policy suggestions are presented in this article.