Carbon-coated CaWO4 nano-crystalline phases have been synthesized by ambient temperature solution precipitation method, characterized by X-ray diffraction, SEM and thermogravimetry and their electrochemical properties were studied versus Li metal. Galvanostatic cycling at a current of 60mA/g in the voltage range 0.005–3.0V on the 5wt.% C-coated CaWO4 gave a reversible capacity of 230±5mAh/g corresponding to 2.5mol of Li, which is almost stable from 20 to 50 cycles. Under the same conditions, the 10wt.% C-coated CaWO4 showed a capacity of 355±5mAh/g (3.8mol of Li) during the initial cycles, but the capacity degraded at a rate of 1.6mAh/g per cycle in the range 5–100 cycles. A good operating voltage range was found to be 0.005–3.0V with average discharge and charge potentials being 0.6 and 1.3V, respectively. Coulombic efficiency in all cases was 96–98%. Cyclic voltammograms compliment the galvanostatic results. Impedance spectral data on the 10wt.% C-coated CaWO4 at different voltages during the first and 20th discharge–charge cycle have been interpreted in terms of the variations in the bulk and charge-transfer resistances of the composite electrode. A reaction mechanism involving the formation/decomposition of the oxide bronze, ‘Li x WO y ’ has been proposed to explain the electrochemical cycling.