Industry 5.0 has introduced a novel interpretation of sustainable supply chains (SSCs) that emphasizes the importance of building a transparent and trustworthy network that can be continuously monitored and controlled through stakeholder collaboration as well as the use of advanced, intelligent machinery. The ultimate goal of SSCs is to meet specific economic, social, and environmental standards. The implementation of blockchain technology can significantly improve the reliability, efficiency, and security of the information exchanged among stakeholders in SSCs. However, these stakeholders inevitably possess varying informational advantages and exhibit divergent perspectives regarding the adoption of blockchain technology. This paper thus aims to examine the impediments to the adoption of blockchain technology in the context of SSCs with the goal of promoting blockchain adoption. To achieve this objective, this study analyzes the barriers to blockchain adoption from the perspectives of various stakeholders in SSCs and constructs a barrier severity assessment model that utilizes group decision-making methods to integrate all stakeholders’ attitudes. This study employs the PEEST (political, economic, environmental, social, and technological) framework to identify 27 barriers to the adoption of blockchain technology. Subsequently, an expertise-based group decision-making approach is used to quantify the prominence of various barriers according to various types of stakeholders. The results indicate that the five most intense barriers are storage constraints, insufficient economic incentives, high integration costs, a lack of functional appeal, and ambiguity regarding data disclosure and public data management regulations. This research makes novel theoretical and practical contributions, as it takes an empirical and all-encompassing approach to identifying obstacles to the adoption of blockchain technology and provides valuable insights for policymakers and practitioners to reference in overcoming these obstacles.