Cement-based batteries (CBBs) are an emerging category of multifunctional materials that combine structural load-bearing capacity with integrated electrochemical energy storage, enabling the development of self-powered infrastructure. Although previous reviews have explored selected aspects of CBB technology, a comprehensive synthesis encompassing system architectures, material strategies, and performance metrics remains insufficient. In this review, CBB systems are categorized into two representative configurations: probe-type galvanic cells and layered monolithic structures. Their structural characteristics and electrochemical behaviors are critically compared. Strategies to enhance performance include improving ionic conductivity through alkaline pore solutions, facilitating electron transport using carbon-based conductive networks, and incorporating redox-active materials such as zinc–manganese dioxide and nickel–iron couples. Early CBB prototypes demonstrated limited energy densities due to high internal resistance and inefficient utilization of active components. Recent advancements in electrode architecture, including nickel-coated carbon fiber meshes and three-dimensional nickel foam scaffolds, have achieved stable rechargeability across multiple cycles with energy densities surpassing 11 Wh/m². These findings demonstrate the practical potential of CBBs for both energy storage and additional functionalities, such as strain sensing enabled by conductive cement matrices. This review establishes a critical basis for future development of CBBs as multifunctional structural components in infrastructure applications.