Lithium cuprate (Li 2 CuO 2 ) was obtained by a solid state reaction and a subsequent ball milling process; then, the samples were characterized structurally and microstructurally. Additionally, both the Li 2 CuO 2 ball milled and the solid state samples, for comparison purposes, were tested in the CO 2 chemisorption process at moderate and low temperatures under different reaction conditions: (i) at moderate CO 2 pressure and (ii) in the presence of water vapor. In both cases, the textural and microstructural properties of the ball milled Li 2 CuO 2 samples showed excellent CO 2 chemisorption properties which are significantly enhanced due to CO 2 pressure effects or the presence of water vapor. All these results were attributed to the textural and morphological changes evidenced in the samples. The observed surface area increments show preponderant effects during CO 2 chemisorption at low and moderate temperatures.