This research employed a behavioral model to confirm and elucidate the critical influence of place attachment, destination involvement, and ambivalent emotion on responsible tourism behaviors. A total of 415 questionnaires were collected from tourists visiting Penghu Island in Taiwan. Following data analysis using structural equation modeling, the results suggested that place attachment, destination involvement, and ambivalent emotion critically impact responsible tourism behaviors, and that place attachment is negatively related to ambivalent emotion. In addition, ambivalent emotion was found to mediate the relationship between place attachment and responsible tourism behaviors. Finally, implications for the promotion of sustainable tourism development were thoughtfully provided based on these findings.