Industry 5.0 places human-centricity, sustainability, and resilience at the core of next-generation enterprise systems. Blockchain has been increasingly recognized as a potential enabler of this transition due to its decentralized architecture, transparency, and trust-enhancing capabilities. Yet, existing literature on enterprise systems remains fragmented in positioning blockchain’s role in enabling these foundational pillars. To address this knowledge gap, we screened and examined 11 peer-reviewed journal articles published between 2019 and 2024 using a scoping review methodology. We adopted the three pillars as our analytical lens. Results showed that blockchain, to some extent, can enable enterprise systems transitions to fulfill the core values of Industry 5.0. Two exemplar success stories, one in maritime logistics and one in healthcare, demonstrate feasibility but underscore unresolved scalability limits. Also, the results reveal issues needing further research and development, such as energy–latency trade-offs that hinder green transitions, underdeveloped governance models for human-in-the-loop decision-making, and fragile cross-chain interoperability that threatens operational resilience. Future research on the adoption of blockchain in enterprise systems must consider energy-efficient consensus protocols, standardized blockchain-IoT interfaces, and ethically grounded governance frameworks. Also, future research should include the development of ethical frameworks to ensure transparency, fairness, and explainability. Drawing on these insights, we outline a research agenda to move the discourse from conceptual promise to industrial practice.