Blockchain technology (BCT) has emerged as a promising disruptive technology with significant applications in the agri-food supply chain (AFSC). This paper reviews the BCT’s research trends, benefits, challenges, and applications in AFSC through systematic literature network analysis (SLNA). A total of 187 articles were selected through a systematic literature review of different reputed databases, and citation network analysis was carried out using “VoSviewer” software. The information related to annual scientific production, country-specific production, type of article, subject area and the most relevant sources was analysed using “Biblioshinny” software. The outcomes reveal prominent benefits, including traceability and transparency, immutability, trust, and decentralization. On the other hand, policy and regulations, scalability issues, less skilled human resources, high investment, and interoperability hinder blockchain implementation. Smart contracts, cybersecurity, food safety, and public distribution systems are some of the identified applications of blockchain technology, thus enhancing agri-food supply chains. Various blockchain-based frameworks in AFSC are also discussed in this review. This review offers insights into how findings may guide practitioners and researchers in developing appropriate BCT systems for AFSC. It also provides practical implications and future research directions on the theme.