A micro-fibrous organic electrode has been prepared by electrospinning process using poly(2,2,6,6-tetramethylpiperidinyloxy-4-ylmethacrylate) (PTMA), poly(vinylidene fluoride-co-hexafluoropropylene) (P(VdF-HFP)) and carbon black powder. The micro-fibrous PTMA electrode (MPE) film is investigated by FT-IR, TGA, SEM, TEM and electrochemical tests. The MPE shows excellent rate-capability and cycle performance. The MPE based lithium cell displays a high discharge capacity of 111 mAh g(-1) at 1C. Even at a high current density of 50C, the MPE cell presents a discharge capacity of 109 mAh g(-1). Moreover, the MPE have remarkably improved the volumetric capacity (209 mAh cm(-3) at 10C) compared with a nano-fibrous PTMA electrode. The excellent electrochemical performance is ascribed to the microstructure that promotes fast ion transport through short diffusion pathways and at the same time facilitates electron transport. (C) 2013 Elsevier B.V. All rights reserved.