Si, when compared to conventional graphite, offers an order-of-magnitude improvement as a high capacity anode material for Li-ion batteries. Despite significant advances in nanostructured Si-based anodes, the formation of stable Si anodes remains a challenge, due to the significant volume changes that occur during lithiation and delithiation. Si/graphene composites, with graphene sheets and Si nanoparticles bound in a dispersion obtained by a self-assembly technique using non-covalent electrostatic attraction (following thermal processing to remove residual organic material) are used to prepare Si-based anodes for use in Li-ion batteries. A mesoporous structure, obtained by further thermal processing is able to accommodate large Si nanoparticle volume changes during cycling, thereby facilitating Li-ion diffusion within the electrode. Morphological analysis showed that Si nanoparticles are homogeneously distributed on the graphene sheets, which is thought to account for the excellent electrochemical performance of the resulting Si/graphene composite. A composite containing Si 67.3 wt% exhibits a greatly improved capacity and cycling stability in comparison with bare Si in combination with the thermal reduction of a simple mixture of graphene oxide and Si nanoparticles without electrostatic attraction (Si content = 64.6 wt%; capacity of 512 mAh g−1 in 40th cycle).