Electricity plays an important role in economic and social development. China’s coal-based power generation structure emits a large quantity of greenhouse gases. Improving electricity consumption efficiency is an important measure for energy conservation and emission mitigation. With this in mind, this study analyzes the influencing factors of electricity consumption and estimates the electricity consumption efficiency by considering the role of structural changes in China’s 30 provinces over the period 2006–2015. The following findings are obtained: (1) Per capita income, urbanization, population, the proportion of secondary industry, and electricity price have significant impacts on electricity consumption. (2) The optimization of industrial structure is conducive for improving the electricity consumption efficiency and has a significant impact, while the improvement in electrification level will lead to a decrease in efficiency score during the study period. (3) There are significant differences in electricity consumption efficiency with a range from 0.372 to 1.000, depending on different model specifications, regions, and years. This paper sheds new light on the electricity demand and its efficiency. Based on these findings, this paper proposes some targeted policy recommendations.