<p>The rapid evolution of lithium-ion batteries (LIBs) has profoundly transformed modern energy storage technologies, enabling widespread applications from portable electronics to electric vehicles and large-scale grids. However, the growing demand for higher energy density, improved safety, and longer service life necessitates the development of advanced electrode materials beyond conventional graphite. Among the various strategies explored, graphene and metal–organic frameworks (MOFs) have attracted particular attention owing to their complementary properties, including high electrical conductivity, tunable porosity, and structural versatility. The integration of MOFs with graphene into composite anodes has recently emerged as a compelling approach to enhance lithium-storage performance by combining robust structural stability with efficient electron and ion transport pathways. In this review, we first trace the historical development of LIBs and summarize the fundamental components and storage mechanisms of conventional systems. We then present a systematic overview of anode materials, with a focus on the storage mechanisms of graphene and MOFs, followed by a comprehensive discussion of MOF/graphene-based composite anodes and their recent progress. By consolidating advances across material design, performance optimization, and mechanistic understanding, this review highlights the advantages and challenges of MOF/graphene hybrids. Finally, we provide perspectives on future directions for the rational design of high-performance anodes, aiming to inspire the next generation of lithium-ion batteries with enhanced capacity, durability, and safety.</p>