Electricity generation in China mainly depends on coal and its products, which has led to the increase in CO2 emissions. This paper intends to analyze the current status of CO2 emissions from electricity generation in China during the period 1991–2009, and apply the logarithmic mean Divisia index (LMDI) technique to find the nature of the factors influencing the changes in CO2 emissions. The main results as follows: (1) CO2 emission from electricity generation has increased from 530.96Mt in 1991 to 2393.02Mt in 2009, following an annual growth rate of 8.72%. Coal products is the main fuel type for thermal power generation, which accounts for more than 90% CO2 emissions from electricity generation. (2) This paper also presents CO2 emissions factor of electricity consumption, which help calculate CO2 emission from final electricity consumption. (3) In China, the economic activity effect is the most important contributor to increase CO2 emissions from electricity generation, but the electricity generation efficiency effect plays the dominant role in decreasing CO2 emissions.