The performance of V2O3 is threatened as a result of relatively sluggish electrons/ion transportation and structural pulverization in lithium-ion batteries. The rational design of the electrode structure to exhibit great lithium storage of V2O3 is crucial. In this work, we report stable composite electrodes by integrating V2O3 nanoparticles with an uneven carbon-coated stainless-steel oxide (V2O3/C/SS) current collector via an in-situ growth method. They allow fast electrical conductivity through the carbon coating and reduction strategy. Meanwhile, the small nanoparticle size of V2O3 on V2O3/C/SS as well as the undestroyed 3D V–V skeleton are helpful to Li-ion diffusion. The weak interaction between Li ions and V2O3 achieves fast and high Li storage behavior, which proves by electrochemical kinetics analysis and DFT calculation. The electrode delivers high rate capacitive and long cycling stability with 564 mAh g-1 and 310 mAh g-1 at 100 mA g-1 and 1 A g-1, respectively, and a specific capacity of 118 mAh g-1 is achieved after 1000 cycles at 5 A g-1. The excellent electrochemical performance may be ascribed to the unique design for effective electron and Li-ion transportation. This work offers a new prospect for the development of highperformance binder-free V2O3-based electrodes.