In the quest for an electroplated selective black coating stable to 500 °C in air, black cobalts have been prepared by three techniques to yield (a) plated cobalt sulphides, (b) plated cobalt oxide‐hydroxide, and (c) cobalt oxide prepared by thermal oxidation of electropolated cobalt metal. The optical properties of the various coatings are analyzed before and after exposure to air for extended periods of time at temperatures in the 300 °–500 °C range. The sulfide black cobalt is not acceptable as a high‐temperature selective absorber due to severe thermal degradation. The plated oxide is a good selective absorber to about 400 °C, and the thermally oxidized black to a slightly higher temperature, but degrades at 500 °C. Structure studies via scanning electron microscopy (SEM), Auger electron spectroscopy (AES), and x‐ray photoemission spectroscopy (XPS) are reported which yield a full account of the coating chemistry before and after heating. The studies reveal that the high solar absorptance of the acceptable black cobalt coatings is due to a continuation of a porous outer layer grading into nondense oxides of cobalt; either CoO or Co3O4, depending on the film. Absorption is intrinsic but not due to metal particles as in black chrome. A limited amount of optical degradation occurs upon heating the oxide black cobalt in air due to oxidation of hydroxide. However, the major degradation problem is shown to be substrate oxidation in contrast to black chrome where film oxidation is the principal problem.