Drawn to the unique natural and geographical advantages of ecotourism scenic areas, tourists can roam the natural environment and, at the same time, promote the sustainable development of the scenic area’s ecology. As a result, ecotourism has gradually become a popular type of tourism. Tourists’ perceived authenticity, perceived values, revisit intentions, and environmentally responsible behaviors, which are important variables in understanding their cognition and behaviors, have received extensive attention from scholars. However, few studies have combined tourists’ perceived authenticity, perceived values, revisit intentions, and environmentally responsible behaviors in the context of ecotourism. Taking Huangshan World Natural and Cultural Heritage Site in Anhui, China, as a case study, this study explored the relationship between the perceived authenticity and perceived values of ecotourists, and the respective relationships of perceived authenticity and perceived values with revisit intentions and environmentally responsible behaviors. A survey research method was employed, and the structural equation modeling technique was used to determine the relationships among variables. The results indicated that the perceived authenticity of ecotourists had a significant positive impact on their perceived values. Tourists’ perceived authenticity and perceived values significantly and positively affected their revisit intentions and environmentally responsible behaviors, respectively, while their perceived values played a mediating role in the impact of perceived authenticity on revisit intentions and environmentally responsible behaviors. Theoretically, this study introduces the concept of perceived authenticity into ecotourism, expands the research scope of perceived values, and fills the gaps in the research regarding the impact of perceived authenticity on environmentally responsible behaviors. Practically, it will assist tourism managers in developing a strategic plan for protecting the unique natural resources and cultural customs of scenic spots, producing a valuable interactive experience, and enhancing the collaborative decision-making process, which will lead to the sustainable development of ecotourism destinations.