This paper explores the relationship between Internet use, environmental risk perception, government performance perception, and pro-environmental behaviors. Survey data from the Chinese General Social Survey 2013 was used to test relevant hypotheses. The results show that: (1) Internet use has significant positive effects on environmental risk perception and pro-environmental behaviors. (2) Internet use and environmental risk perception have significant negative effects on public perception about the government’s environmental performance. (3) Government performance perception has a significant positive effect on pro-environmental behaviors and negatively mediates the effect of Internet use and environmental risk perception on pro-environmental behaviors. The findings suggest that increasing the government’s environmental performance exposure can stimulate public engagement in pro-environmental behaviors, thus facilitating the implementation of environmental policies requiring citizen engagement.