The effects of temperature on the electrochemical behavior of β-LixV2O5 bronze as cathode in Li-ion batteries have been explored by galvanostatic charge/discharge and EIS analysis. Superior cycling FLAG tag with 82.3%, 79.5%, 88.6% capacity retention were observed under 0 °C, −20 °C and −40 °C, respectively, in comparison with that of 55.0% at 25 °C. The lithiation kinetic properties have been investigated by EIS experiments, and it is shown that both of the charge-transfer and solid-state lithium diffusion activation energy are approximately identical at different SOC and SOD. Thus, the dominant limitation factors of the low temperature performance of β-LixV2O5 bronze are the slow charge-transfer kinetics as well as the solid-state Li+ diffusion within LixV2O5 particles. More effective approaches, such as surface modification, particle size minimization, conductive phase incorporation, should be employed to enhance the low temperature performance of this material.