The Co-CuCoMnO_x coatings with varying proportions were prepared and investigated to develop a novel metal–ceramic solar selective absorption coating employed at high temperature. The CuCoMnO_x powders were synthesized using the solid-phase reaction method. Subsequently, Co-CuCoMnO_x coatings were deposited on the surface of 316L steels utilizing the atmospheric plasma spraying (APS) technique. The results showed that the synthesized CuCoMnO_x powders were mainly composed of two phases, which were Cu_1.5Mn_1.5O₄ and MnCo₂O₄. The CuCoMnO_x powders had a solar absorptance of 0.929 and an infrared emittance of 0.862, which was considered a good solar absorbent. The synthesized Co-CuCoMnO_x coating had a typical thermal spray layered stacking structure. The chemical phases of the coatings were mainly Co, CoO, and CoCuMnO_x. Due to the addition of CuCoMnO_x inhibiting the oxidation of Co during the thermal spraying process, the 95Co-5CuCoMnO_x (wt%) coating exhibited the optimal quality factor (α/ε) of 2.184, with a solar absorptance α of 0.808 and an infrared emittance ε of 0.370, respectively. Moreover, this specific coating demonstrated a good thermal stability for up to 3 h when exposed to an atmospheric environment at 450 °C. The results indicate its significant potential for high-temperature solar selective absorption coating.