Tourists’ environmentally responsible behavior (TERB) is one of the key areas in tourism as it concerns tourism sustainability that further influences a destination’s competitiveness and image. This study sought to deepen the formation of TERB through tourists’ degree of environmental perception, mediated by their feeling of awe towards the environment, and moderated by their level of face consciousness. Data were collected from tourists in Tibet and the findings indicated that awe exerted partial mediation on the tourists’ perception-behavior relationship. Furthermore, face consciousness moderated the mediated relationship of humanistic environmental perception, awe, and TERB. This study adds value to existing tourism studies by revealing the influences of awe on constructing tourists’ attitude in sustainable tourism. From a practical perspective, the findings offer insights for destination management organizations (DMOs) in promoting tourists’ environmentally responsible behavior that fosters sustainable tourism development.