Copper manganese composite (hopcalite) catalyst has been widely explored for low-temperature CO oxidation reactions. However, the previous reports on the stabilization of such composite catalysts have shown that they deactivated severely under moist conditions. Herein, we developed an α-MnO2 nanorod-supported copper oxide catalyst that is very active and stable for the conditions with or without moisture by the deposition precipitation (DP) method. Incredibly, the CuO/MnO2 DP catalyst (with 5 wt % copper loading) achieves superior activity with a reaction rate of 9.472 μmol–1·gcat–1·s–1 even at ambient temperatures, which is at least double times of that for the reported copper-based catalyst. Additionally, the CuO/MnO2 DP catalyst is significantly more stable than the copper manganese composite catalysts reported in the literature under the presence of 3% water vapor as well as without moisture. A correlation between the catalytic CO oxidation activity and textural characteristics was derived via multitechnique analyses. The results imply that the superior activity of the CuO/MnO2 DP catalyst is associated with the proper adsorption of CO on partially reduced copper oxide as Cu(I)–CO and more surface oxygen species at the interfacial site of the catalyst.