In this paper, glucose and carbon nanotubes (CNTs) modified Li3V2(PO4)3 have been synthesisd via a carbon thermal reduction method. The structure of Li3V2(PO4)3 has been confirmed by X-ray diffraction, Raman spectra, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy. The CNT modified Li3V2(PO4)3 materials combined with the synthesized electrolyte, overcomes the limitations of Li-ion battery at low temperature. The synthesized electrolyte is made up of 1.2 M LiPF6 dissolved in EC:DMC:EMC (1:1:1 in volume) with vinylene carbonate (VC) and propylene sulfite (PS) as the additive agents. The electrochemical behaviors of the cells have been evaluated by electrochemical test over the temperature range from 25 to −20 ○C. The specific capacity is 116.2, 108.2, 103.7, 96.3, 86.1 mAh g−1 at 0.5 C, 1 C, 2C, 5 C, 10C between 3.0 and 4.3 V at −20 ○C. After 300 cycles the capacity retention still reached 97% even at −20 ○C. The excellent rate capability and low temperature performance are attributed to the synergistic effect between the CNTs and the synthesized low temperature electrolyte.