A 3V lithium ion battery with LiCoPO4 and zero-strain Li4Ti5O12 as insertion material is constructed and investigated. Electrochemical tests show that the full cell displays two operation voltage plateaus (3.24V and 3.17V). Further, the effects of the theoretical capacity matchup ratio between cathode and anode in the LiCoPO4/Li4Ti5O12 cell system on the electrochemical properties are firstly investigated. The LiCoPO4/Li4Ti5O12 cell delivers a highest initial discharge capacity of 135.6 mAh g−1. A 3.2V lithium-ion battery would further extend the application of lithium ion batteries in energy conversion and storage applications.