This chapter explores the role of blockchain technology in the agrifood sector. Through case studies of blockchain applications in agricultural supply chains, the work examines blockchain’s role in food sustainability by enhanced transparency, traceability, and resource efficiency while supporting environmental, social, and governance (ESG) initiatives in the agrifood sector. The chapter shows that, in addition to traceability, blockchain technology promotes consumer empowerment by enabling direct product verification, improving purchasing decisions, and transforming the supply chain into a trust-based, participatory network. Furthermore, the analysis presents blockchain as a novel source of value creation in markets by differentiating products and brands through transparency, engagement, and shared values. The work also presents an in-depth analysis of blockchain adoption trends among regional areas, highlighting synergies with other digital technologies such as artificial intelligence (AI) and the Internet of Things (IoT) to enhance system scalability and interoperability. Challenges related to blockchain adoption in the agri-food sector are also presented, focusing on regulatory, technological and market-related challenges, to guide companies in leveraging the power of blockchain to shape an agriculture 5.0 ecosystem.