A three-dimentional(3D) long-range networking Li3V2(PO4)3/C fiber membrane was fabricated by a modified electrospinning method and a hot-press calcination process. The combined use of polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP) promotes the growth of Li3V2(PO4)3 crystals on the surface of the conductive carbon fibers. The adopted hot-press process is favorable to achieve a flexible 3D long-range networks. The Li3V2(PO4)3/C fiber membrane calcined at 800°C for 20h with a high specific surface area of 186.4m2/g and a wide pore size distribution can be used as self-standing, binder-free cathodes and exhibits excellent electrochemical performances. The discharge capacity is up to 196.8, 150.4 and 145.2 mAh/g at the current density of 0.1C, 5C and 10C, respectively. After the rate tests, the Li3V2(PO4)3/C fiber membrane cathode still exhibits an excellent cycle stability at 5C with a discharge capacity of 143.4 mAh/g after 850 cycles. These high performances are ascribed to the enhanced electronic and ionic conductivities owing to the 3D long-range conductive networks, well-crystallized Li3V2(PO4)3 particles in-situ grown on the surface of carbon fibers and the novel binder-free, self-standing structural characterics.