A free-standing LiFePO4/carbon nanofiber hybrid (LFP/CF) electrode with (010)-oriented LiFePO4 nanocrystals was in-situ constructed by a one-pot electrospinning method. It is found that poly (vinylpyrrolidone) (PVP) can regulate the growth of (010)-face-orientated LiFePO4 crystals partly. As a model material, the optimal (010)-manifest LiFePO4/carbon nanofibers cathode exhibits a discharge capacity of 152 mA h g(-1) at 0.5C after 500 cycles with capacity retention of 98.2% and superior rate performance of 108.6 mA h g(-1) at 5C. The excellent performance can be ascribed to the well-designed 3D conductive network, fast Li-ion diffusion path, and porous structure for electrolyte penetration. This route provides an efficiency strategy with low cost and one-step process for the preparation of free-standing (010)-manifest LiFePO4/carbon nanofiber cathode material, and can also be extended to other olivine materials. (C) 2019 Elsevier Ltd. All rights reserved.