This research used the SBM model based on undesirable outputs to measure the static environmental efficiency of Western China under carbon emission constraint from 2000 to 2012. The researchers also utilized the Malmquist index to further analyze the change tendency of environmental efficiency. Additionally, Tobit regression analysis was used to study the factors relevant to environmental efficiency. Practical solutions to improve environmental quality in Western China were put forward. The study showed that in Western China, environmental efficiency with carbon emission constraint was significantly lower than that without carbon emission constraint, and the difference could be described as an inverse U-shaped curve which increased at first and then decreased. Guang-xi and Inner Mongolia, the two provinces met the effective environmental efficiency levels all the time under carbon emission constraint. However, the five provinces of Guizhou, Gansu, Qinghai, Ningxia and Xinjiang did not. Furthermore, Ningxia had the lowest level of environmental efficiency, with a score between 0.281-0.386. Although the environmental efficiency of most provinces was currently at an ineffective level, the environmental efficiency quality was gradually improving at an average speed of 6.6%. Excessive CO2 emission and a large amount of energy consumption were the primary factors causing environmental inefficiency in Western China, and energy intensity had the most negative impact on the environmental efficiency. The increase of import and export trade reduced the environmental efficiency significantly in Western China, while the increase of foreign direct investment had a positive effect on its environmental efficiency.