Pro-Environmental Behavior (PEB) of residents can greatly alleviate the threat of environmental pollution to human living environment and promote sustainable development of the society. Cross-cultural studies show that there are significant differences in PEB among countries with different cultural backgrounds. Even within the same country or region, individual cultural values are not identical. So, can various individual cultural values impact PEB differently? To answer this question, this paper investigates the mechanism on how cultural value differences affect residents' PEB, based on Hofstede's cultural model. Following an analysis of 475 questionnaires from residents, the results show that Hofstede's five dimensions of cultural value can significantly impact public-and/or private-sphere PEB. Among them, collectivism and long-term orientation of residents have positive effects on both public-and privatesphere PEB and uncertainty avoidance has a negative impact. Besides, masculinity only affects the public-sphere PEB, and power distance affects neither private-nor public-sphere PEB. In addition, three social-demographic characteristics including gender, age, and educational level have a significant moderating effect on the relationship between cultural values and PEB. These findings can provide useful recommendations for policy makers to draft PEB guidelines and incentive policies based on the differences in cultural values of their residents.