The Library and Information Science (LIS) community has started discussing some possible uses of Blockchain (BC) technologies in solving library-related problems and increasing the overall efficiency of libraries. This study aimed to systematically collect and review the relevant literature to comprehend the scope of BC for libraries, its benefits, as well as the challenges, and implications related to its use. The authors explored six reputed databases (Web of Science, Scopus, LISTA (Library, Information Science and Technology Abstracts), LISA (Library and Information Science Abstracts), IEEE (Institute of Electrical and Electronics Engineers), and Google Scholar) to conduct this review. This study was conducted using the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines. After the final data extraction, 21 documents were considered eligible for the systematic review. A systematic review of the selected works indicated that the usage of BC in libraries ranged from record-keeping to processing payments and ensuring security and transparency. Some of the opportunities that can be hunted from BC were the elimination of corruption, enhanced security, improved efficiency of services, and better time management. Literature also indicated that a lack of awareness of technology, unskilled staff, and financial constraints could impede the adoption of BC by libraries. It is hoped that this study would provide a holistic overview of BC technologies for libraries, thus improving the effectiveness of the decision-makers. This study is first that collected (systematically) and reviewed the literature on BC usage in libraries. The review will help educational institutions and library professionals understand the usage, challenges, and benefits of BC for libraries.