It is not that the public is unwilling to participate in environmental protection, but rather that they lack the appropriate information. The media offers an alternative explanatory pathway to understanding citizens’ willingness to pay (WTP) for environmental governance, but the existing literature still lacks empirical studies on this topic and the intermediate mechanisms. Adopting an environmental communication perspective, this paper divided the environmental effects of media into two dimensions: knowledge growth and responsibility cultivation, and conducted an empirical analysis on whether, and how, media use affected citizens’ WTP, based on data from the China General Social Survey 2018 (hereafter, CGSS2018). The findings found that the frequency of media use significantly increased citizen’s WTP, in which individual environmental responsibility rather than environmental knowledge played a mediating effect; i.e., media use increased individuals’ WTP by increasing the public’s environmental responsibility. Furthermore, this study discovered that traditional media use had a significant effect on the citizens’ WTP, again verifying the mediating effect of individual environmental responsibility, while new media use did not have such a communication effect. This study extends the theories related to pro-environmental behaviors, and provides practical implications for the government to promote environmental governance and sustainability.