Electrospinning is firstly used to one-pot synthesis of Li3VO4@C nanofibers in a large scale. Although with the presence of organic sources in synthesis process, the pure phase Li3VO4 with superior nanofibrous morphology is still successfully obtained through adjusting different heat treatment processes and different vanadium sources. The preparedLi(3)VO(4)@C nanofibers exhibit a unique structure in which nanosized Li3VO4 particles are uniformly embedded in amorphous carbon matrix. Compared with Li3VO4/C powder, Li3VO4@C nanofibers display enhanced reversible capacity of 451 mAh g(-1) at 40 mA g(-1) with an increased initial coulombic efficiency of 82.3%, and the capacity can remain at 394 mAh g(-1) after 100 cycles. This superior electrochemical performance can be attributed to its unique structure which ensures a high reactivity by nanosized Li3VO4, more stable electrode/electrolyte interface by carbon encapsulation, improved electronic conductivity and buffered volume changes by flexible carbon matrix. The electrospinning technology provides an effective method to obtain high performance Li3VO4 as a promising anode material for lithium-ion batteries. (C) 2017 Science China Press. Published by Elsevier B.V. and Science China Press. All rights reserved.