With the rapid development of information technology, pro-environmental behavior (PEB) also presents new features in the practice of environmental governance under big data. According to the value norm theory and expectancy theory of motivation, the influence mechanism and path effects of environmental awareness, environmental attitude, expected performance of public participation for PEB were studied by constructing the structural equation modeling in this paper. The results of empirical study in 31 provinces of China show that: (1) Environmental awareness and environmental attitude will influence PEB through the mediating variable of “expected performance of public participation”. (2) The mediating effect of expected performance of public participation on environmental awareness and PEB is complete mediating. (3) The mediating effect of expected performance of public participation between environmental attitude and PEB is partial mediating. Environmental attitude can either directly affect PEB, or indirectly affect PEB through affecting the expected performance of public participation. Based on the above results, some countermeasures are put forward.