Limited research has addressed the potential of Web 3.0 to facilitate the green supply chain and support sustainable development goals. Although some studies have suggested the efficiency of Web 3.0 in promoting a green supply chain, lack empirical evidence explaining how this efficiency is generated remains scarce. Therefore, the objective of this study is to investigate this matter. By drawing upon relevant literature and leveraging the natural resource‐based view, a conceptual model is constructed and validated using partial least squares structural equation modeling (PLS‐SEM). The analysis reveals that Web 3.0 can foster the formation of consensual thinking through its decentralized mechanism. This, in turn, enables firms to generate perceived value based on the efficiency of consensual thinking, leading to an increased intention to build mutual trust and facilitate green knowledge sharing among firms. Furthermore, the controllability provided by a permissioned mechanism enhances information security, guiding mutual trust among firms to evolve into trustless cooperation. As a result, firms exhibit full trust in each other, facilitating smoother green knowledge sharing. The influence of mutual trust and trustless cooperation in promoting green knowledge sharing contributes to the resilience of the supply chain and ultimately leads to superior green performance, contributing to environmentally sustainable development. This study provides valuable insights into the integration of the green supply chain and Web 3.0, filling a gap in the existing literature.