In this original work, series of the CuO–V2O5 oxides, such as CuV2O6, Cu2V2O7 and Cu5V2O10 have been synthesized and evaluated as possible candidate cathode materials in high voltage Li thermal batteries. The structure and morphology have been determined and the electrochemical properties at room temperature and elevated temperatures (525 °C) against Li metal alloy have been investigated. At room temperature, an increase in copper content in the vanadate has been found to provoke a gradual negative shift of the operating voltage plateau vs. Li metal. Room temperature discharge capacity in a Li cell is relatively high and can exceed 350 mAhgr−1. In a thermal Li cell configuration and at an elevated temperature a voltage plateau of 3.4 V at a current load of 100 mA g−1 was achieved and a voltage plateau of 2.5 V was recorded with a current load of as high as 310 mA g−1. Thus, copper-vanadate materials may be regarded as promising short time – high voltage cathodes for thermal Li batteries.