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.