The development of 1D porous electrodes with high-rate capability and long cycle-life is a central issue for electrochemical energy storage. Herein, the 1D highly porous Li3V2(PO4)(3)/C nanofibers for lithium-ion batteries cathode have been designed and successfully fabricated via a facile electrospinning-assisted solid-state method. Benefiting from the well-defined 1D porous structure, the as-fabricated product displays excellent electrochemical performance when used as cathode for lithium-ion batteries in the potential range of 3.0 and 4.8 V. It exhibits high reversible capacity of 191 mAh g(-1) at a low rate of 0.1 C, superior rate performance (110 mAh g(-1) at 20 C) and good cycle-life stability (94.5% capacity retention over 120 cycles at 20 C). Therefore, this 1D porous Li3V2(PO4)(3)/C is a promising cathode material for high-performance lithium-ion batteries and the synthetic strategy presented in this work can be further used to prepare other electrodes in energy storage.