The electrochemical performance of mixed oxides, Ca2Fe2O5 and Ca2Co2O5 for use in Li-ion batteries was studied with Li as the counter electrode. The compounds were prepared and characterized by X-ray diffraction and SEM. Ca2Fe2O5 showed a reversible capacity of 226mAh/g at the 14th cycle and retained 183mAh/g at the end of 50 cycles at 60mA/g in the voltage window 0.005–2.5V. A reversible capacity in the range, 365–380mAh/g, which is stable up to 50 charge–discharge cycles is exhibited by Ca2Co2O5 in the voltage window, 0.005–3.0V and at 60mA/g. This corresponds to recycleable moles of Li of 3.9±0.1 (theoretical: 4.0). Significant improvement in the cycling performance and attainable reversible capacity were noted for Ca2Co2O5 on cycling to an upper cut-off voltage of 3.0V as compared to 2.5V. Coulombic efficiency for both compounds is >98%. Electrochemical impedance spectroscopy (EIS) data clearly indicate the reversible formation/decomposition of polymeric surface film on the electrode surface of Ca2Co2O5 in the voltage window, 0.005–3.0V. Cyclic voltammetry results compliment the galvanostatic cycling data.