The rapid advancement of portable electronics, electric vehicles, and renewable energy systems has heightened the global demand for high-performance energy storage solutions. While lithium-ion batteries (LIBs) have become the dominant technology, their performance is constrained by the limitations of traditional graphite anodes, such as low specific capacity, poor rate capability, and degradation during long-term cycling. This review explores the transformative potential of graphene, a two-dimensional allotrope of carbon as a next-generation anode material in LIBs. Graphene’s exceptional properties, including high surface area (2600 m²/g), superior electrical and thermal conductivity, mechanical strength, and theoretical specific capacity (~744 mAh/g), position it as a compelling candidate to overcome the shortcomings of graphite. The paper discusses various synthesis strategies, such as chemical vapor deposition, exfoliation techniques, and redox methods, emphasizing their scalability, quality, and structural control. Further, it explores hybrid architectures like silicon–graphene composites and 3D graphene frameworks, which offer enhanced lithium-ion diffusion, volumetric stability, and improved solid electrolyte interphase (SEI) formation. Performance metrics such as energy density, charge/discharge rates, and cycling stability are critically analyzed with evidence from recent studies. Despite the impressive advancements, commercial challenges including, high production costs and scalability issues remain. However, ongoing research and industrial interest, particularly in electric vehicles and consumer electronics, signal a promising future for graphene-enhanced batteries. This review underscores the pivotal role of graphene in redefining anode technology and highlights future directions to accelerate its transition from lab to market.