A facile citric acid assisted sol-gel combustion method was performed to synthesize cobalt chromite (CoCr₂O₄) ceramic pigment. The effect of the annealing temperature on structure, morphologies, and optical properties of the prepared Co₂O₄ pigments were systematically studied by thermogravimetry, differential thermal analysis, X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM). The results show that Co₂O₄ spinel crystal was achieved after heat treatment of the as-burnt powder at a relatively low temperature (400 °C) and the average crystallite size of the Co₂O₄ pigment increased with the annealing temperature. Furthermore, on the CIE parameters of Co₂O₄ pigment, a* and b* values became much more negative with the annealing temperature due to much more Co²⁺ ions located in tetrahedral sites and much more Cr³⁺. ions located in octahedral sites. Finally, the measured solar absorptance indicates that this ceramic pigment is expected to fabricate the color paint coating for solar absorber application.