Actively promoting pro-environmental behavior not only can effectively reduce degree of environmental pollution, but also is a necessary step for the sustainable development of social economy. Although scholars have had in-depth discussions on influencing factors and promoting mechanism of pro-environmental behavior, research concerning effects of external situational factors on pro-environmental behavior is relatively insufficient, and impacts of natural environment conditions, say, air quality is seldom considered. With the development of China’s economy, industrial growth and advancing urbanization, air quality continues to deteriorate when acid rain, haze and other harsh weathers occur more frequently, seriously affecting and endangering people’s health and daily life. So, does air quality also affect people’s pro-environmental behavior? And if so, how is that impact? What is the internal mechanism? Based on the above questions, this paper designed two studies, in combination with spatial distance, and explored the impacts of air quality on Chinese residents’ pro-environmental behavior. It also demonstrated the internal impact mechanism from the perspective of environmental emotion, and expanded research on impact mechanism of air quality on pro-environmental behavior.