Acid rain has been a great threat to socioeconomic sustainable development of China; therefore, we develop an indicator system based on the sensitivity and adaptive capacity perspectives and employ the TOPSIS (Technique for Order Preference by Similarity to Ideal Solution) approach to investigate the impact of acid rain on socioeconomic vulnerability of China. Some empirical findings are obtained. First, there is significant provincial difference of socioeconomic vulnerability caused by acid rain in China. Specifically, Tibet, Qinghai, and Shanghai are the top three provinces with the largest vulnerability but Inner Mongolia, Xinjiang, and Jilin are bottom of the rankings. Second, adaptive capacity indicators overall appear more important than sensitivity indicators to measure the vulnerability of acid rain, and the most important indicators are population density and output value of agriculture, forestry, animal husbandry, and fishery while GDP per capita ranks the last. Third, upgrading energy structure and reducing outdated capacity in China prove to be effective means to mitigate vulnerability of acid rain, which has been validated in Guizhou and Hunan provinces. Finally, great attention should be attached to the population increase so as to curb the acid rain vulnerability, especially in Beijing and Tianjin. These results present a basis for future acid rain prevention planning and economic development in China.