Based on the theory of relationship quality, the research constructed the impact mechanism model of pro-environmental behaviours by applying tourist’s perceived value as the antecedent variable, while relationship quality (satisfaction and loyalty) was treated as the mediators, and place attachment as a moderator. Surveys were conducted at the Daweishan National Forest Park in Hunan Province, China, with 674 valid questionnaires collected. The empirical results provided evidence that the direct effect of perceived value of tourists on tourists’ pro-environmental behaviours is significantly positive, and the indirect effect of relationship quality (satisfaction and loyalty) between perceived value of tourists. Recommendations and strategies for further research and implementing tourist stratification management are suggested.