We report a novel primary Li-CO2 battery that consumes pure CO2 gas as its cathode. The battery exhibits a high discharge capacity of around 2500 mA h g-1 at moderate temperatures. At 100 °C the discharge capacity is close to 1000% higher than that at 40 °C, and the temperature dependence is significantly weaker for higher surface area carbon cathodes. Ex-situ FTIR and XRD analyses convincingly show that lithium carbonate (Li2CO3) is the main component of the discharge product. The feasibility of similar primary metal-CO2 batteries based on earth abundant metal anodes, such as Al and Mg, is demonstrated. The metal-CO2 battery platform provides a novel approach for simultaneous capturing of CO2 emissions and producing electrical energy. © 2013 The Royal Society of Chemistry.