Tourism, as a new way of industrial poverty alleviation, is of great significance to poverty reduction in border areas. This research takes the Sino–Vietnamese border tourism area as a case study and introduces a sustainable livelihood analysis framework. It collects questionnaire data from Napo County of Guangxi and uses structural equation modeling to analyze the behavioral intention of farmers still willing to participate in tourism after overcoming poverty. Results indicate that (1) participation motivation, participation opportunity, and participation ability had significant positive effects on farmers’ involvement level; (2) farmers’ economic, social, cultural, political, and environmental outcome perceptions had significant effects on their sustainable livelihood outcome perception; (3) farmers’ involvement level had a significant positive effect on their sustainable livelihood outcome perception; (4) the positive effect of the involvement level on behavioral intention failed to pass the significance test; and (5) farmers’ sustainable livelihood outcome perception had a significant positive impact on behavioral intention. Therefore, farmers’ involvement in poverty alleviation through tourism is a complex process of behavior and psychological perceptions.