Lithiated transition metal phosphates with large theoretical capacities have emerged as promising cathode materials for rechargeable lithium-ion batteries. However, the poor kinetic properties caused by their low intrinsic electronic and ionic conductivity greatly hinder their practical applications. In this work, we demonstrate a novel strategy to prepare monoclinic lithium vanadium phosphate nanoparticles implanted in carbon nanofibers as the cathodes of Li-ion cells with high capacity, flexibility, long cycle stability and significantly improved high-rate performance. The composite nanofibers were obtained by electrospinning using polyacrylonitrile and Li3V2(PO4)(3) nanoparticles, followed by annealing and coating with a thin layer of carbon by plasma enhanced chemical vapor deposition. The Li3V2(PO4)(3) nanocrystals with the monoclinic phase were uniformly distributed in the composite nanofibers. The electrochemical performances of the as-prepared binder-free fibrous cathodes were characterized by potentiostatic and galvanostatic tests. At the rate of 0.5 C in the range of 3.0-4.3 V, the composite displayed an initial discharge capacity of 128 mA h g(-1) (96.2% of the theoretical capacity). A discharge capacity of 120 mA h g(-1) was observed even at a high rate of 10 C, and a capacity retention of 98.9% was maintained after 500 cycles at 5 C, indicating excellent high-rate capability and capacity retention. Compared to the control samples without a carbon outer-layer, the composite nanofibers with carbon coating demonstrated much better electrochemical performances. It indicates that the carbon coating can further protect the structural integrity of nanofabric electrodes during the charge/discharge processes without hindering the Li-ion mobility and also can prevent undesired side reactions with an electrolyte, thus greatly improving the rate performance and cyclic stability of the cathode.