During the economic boom, China's government was mainly concerned with economic development; however, numerous environmental problems have arisen. Evidence suggests that Chinese individuals' pro-environmental behavior (PEB) is at a low level in Asia. However, it does not match their high-quality environmental knowledge. In this paper, the database of the Chinese General Social Survey was used to explore the correlation between environmental knowledge and PEB in a broader context. Subsequently, environmental perception and post-materialistic values (PMV) were taken as the mediator and moderator into structural equation modeling, and every variable kept robust and consistent through exploratory factor analysis. The empirical results indicated that: (i) individuals with higher environmental knowledge always show higher passion to PEB; (ii) environmental perception plays a partially mediating role between environmental knowledge and PEB; (iii) PMV moderate the formation of environmental behavior systematically; and (iv) compared with public counterpart, the relation between environmental knowledge and PEB is significantly higher in private environmental behavior. The study results could become the basis for the Chinese government and environmental NGOs to effectively spread environmental knowledge, advocate a post-materialistic lifestyle, and improve the authenticity of online media reports on environmental issues.