To improve the coulombic efficiency of GeO2 electrode, a Cu-containing ternary metal oxide (CuGeO3) was prepared and the electrochemical behavior of Cu component was studied. The GeO2 electrode shows a low coulombic efficiency in the first cycle (43%), which is mainly caused by a poor Ge oxidation kinetics (Ge+2Li2O→GeO2 +2Li+ +2e−). The X-ray absorption spectroscopy (XAS) data illustrate that the Cu component in CuGeO3 is converted to nano-sized metallic Cu in the earlier stage of lithiation but idles thereafter. In contrast, the Ge component in CuGeO3 behaves like the GeO2 electrode. It is converted to nano-sized Ge by a conversion reaction and further lithiated by alloying reaction. The de-lithiation proceeds in the reverse order. The CuGeO3 electrode shows a much improved coulombic efficiency (74%) in the first cycle, which is indebted to a facilitated Ge oxidation with a much reduced electrode polarization. This feature has been explained by the favorable roles provided by the in situ generated nano-sized metallic Cu particles that make such an intimate contact with the nano-sized Ge and Li2O that they can catalyze Li2O decomposition and provide an electronic conductive network for Ge oxidation. A similar favorable effect was observed with the other ternary oxides (FeGeO3 and CoGeO3), wherein the formation of nano-sized metallic Fe and Co can be assumed.