A silicon/graphene composite anode for lithium-ion batteries was fabricated with a high loading of Si by combining surface-modified silicon with graphene. The Si nanopowder was modified by a binder-like organic moeity (1-(bromoethyl) benzene and polyacrylic acid) grafted on the surface of hydrogenated silicon by diazonium chemistry and surface initiated atom transfer radical polymerization. The graphene was produced by electrochemical exfoliation of natural graphite. The optimum composite electrode prepared without a binder, with silicon loading as high as 85 wt% and a mass loading of 1.1 ± 0.1 mg cm−2 yielded a discharge capacity of 1020 mAh per gram of electrode mass (or 1200 mAh per gram of Si) after 586 charge/discharge cycles at a rate of 3.4 A g−1. It showed first cycle Coulombic efficiency of more than 90% in the absence of electrolyte additives at a current rate of 0.05 A g−1.