The energy and storage sector of today's world is constantly facing challenges in terms of the performance, functionality of the fundamental materials. Graphene is a Carbon-based material that is extensively investigated as anode material for rechargeable secondary Lithium-ion batteries (LIBs) because of its amazing superlative properties i.e. mechanical, optical, electrical, thermal, and sensing properties. Graphene has extraordinary electron mobility (2.5×105 cm2 V-1 s-1) and a large surface area (2630 m2g-1) and these interesting properties make it a suitable material for the energy storage device. Also Nanostructure evolution of graphene, its electrochemical performance raised to a new stage. In this review, we focus on the electrochemical performance of graphene and Graphene-based nanocomposite materials in Lithium-ion Batteries and also focuses on the synthesis route of graphene which is used both industrially and commercially.