The frequent occurrence of air pollution and other environmental problems significantly changes the external institutional environment of enterprises. The environmental governance behavior of heavy-polluted enterprises is not only driven by external institutional factors, but also heavily influenced by the internal nature of property right. Taking 377 A-share listed companies in heavy-polluted industry in Shanghai and Shenzhen as the research object, this paper empirically examines the relationship among air pollution, nature of property right and environmental governance behavior of enterprises. The empirical result turns out that there is a positive correlation between the degree of air pollution and the environmental governance behavior of heavy-polluted enterprises, in another word, the more the degree of air pollution, the more effort the heavy-polluted enterprises will make to control the enterprise environment. The nature of property right plays a partial mediating effect role in the relationship between the degree of air pollution and the environmental governance behavior of heavy-polluted enterprises. The conclusions of this paper provide an empirical basis for China to further improve the driving mechanism of environmental governance behavior of heavy polluted enterprises.