The harmonious coexistence of humanity and nature stands as a paramount objective in the global endeavor towards ecological civilization. By vigorously promoting eco-friendly recreational activities within World Agricultural Heritage sites, we can evoke tourists’ emotional understanding and empathy towards environmental protection. This approach presents an optimal solution to the challenges faced in realizing the ecological value of these heritage sites, thereby fostering an even deeper harmony between people and nature. For this study, the Anxi Tie Guan Yin Tea Cultural System, a site of global agricultural heritage significance, was chosen as the case study. Employing structural equation modeling (SEM) analysis, a survey was administered to 452 local tourists for empirical testing. The research reveals several key findings: (1) Tourists’ environmental concern exerts a notably positive influence on their pro-environmental behaviors; (2) both nature empathy and ecological anxiety serve as mediators in the relationship between environmental concern and tourists’ pro-environmental behaviors; (3) furthermore, nature empathy and ecological anxiety exhibit a sequential, or chain, mediation effect between environmental concern and pro-environmental behaviors; and (4) lastly, the impact of nature empathy and ecological anxiety on tourists’ pro-environmental behaviors differs according to gender. Consequently, managers of agricultural heritage sites should aim to evoke tourists’ sense of nature empathy while appropriately stimulating their ecological anxiety, thereby providing guidance for ensuring a harmonious blend of human activities and the ecological environment and ultimately fostering the sustainable development of World Agricultural Heritage sites.