Polymer-functionalized graphene sheets play an important role in graphene-containing composite materials. Herein, functionalized graphene sheets covalently linked with radical polymer, graphene-graft-poly(2,2,6,6-tetramethylpiperidin-1-oxyl-4-yl methacrylate) (G-g-PTMA), were prepared via surface-initiated atom transfer radical polymerization (SI-ATRP). A composite cathode with G-g-PTMA as major active material and reduced graphene oxide (RGO) as conductive additive was fabricated via a simple dispersing-depositing process, and this composite cathode exhibited a relatively high specific capacity up to 466 mAh g(-1) based on the mass of PTMA, which is much higher than the theoretical capacity of PTMA. This extraordinary electrochemical performance is attributed to the fast one-electron redox reaction of G-g-PTMA and surface Faradaic reaction of RGO boosted by G-g-PTMA, which suggested that G-g-PTMA sheets play a dual role in the composite materials, that is, on the one hand provided the fast one-electron redox reaction of PTMA and on the other hand worked as nanofiller for facilitating the surface Faradaic reaction-based lithium storage of RGO.