Although lithium ion battery is known to be an excellent renewable energy provider in electronic markets further application of it has been limited by its notoriously poor performance at low temperature, especially below −20 °C. In this paper, the electrochemical performance of the LiNi1/3Co1/3Mn1/3O2 cathode materials coated by lithium boron oxide (LBO) glass was investigated at a temperature range from 20 to −40 °C. The results show that the LBO coating not only helps to improve the discharge capacity of LiNi1/3Co1/3Mn1/3O2 at room temperature but also increase the discharge capacity retention of the LiNi1/3Co1/3Mn1/3O2 from 22.5% to 57.8% at −40 °C. Electrochemical impedance spectra results reveal that the LBO coating plays an important role in reducing the charge-transfer resistance on the electrolyte–electrode interfaces and improving lithium ion diffusion coefficients. The mechanism associated with the change of the structure and electrical properties are discussed in detail.