Si/Ni3Si-encapulated carbon nanofiber composites are synthesized by a facile one-pot electrospinning method and employed as three-dimensional network structured anode materials for lithium ion batteries. It is demonstrated that the composite exhibited increased cycling performance with a reversible capacity of 1132.4 mAh g(-1) after 200 cycles, which is 45% higher compared to the bare Si. The improved battery performance is attributed to the alloying of Si with Ni, which could effectively alleviate the volume expansion during lithium insertion/extraction. In addition, the formation of one dimensional nanofiber in which Si/Ni3Si nanoparticles are well distributed not only increases the electronic conductivity, but also enhances the mechanical strength of the electrodes, resulting in increased cycle stability. (C) 2016 Elsevier Ltd. All rights reserved.