A series of CuCr₂O₄ spinel ceramic pigments have been successfully synthesized via a facile and cost-effective sol-gel self-combustion method. The reaction mechanism was systematically studied using the corresponding characterization technologies. The results suggested that CuCr₂O₄ spinel ceramic pigments could be obtained at annealing temperature of 600 °C for 1 h, and the size, morphology, and crystallinity of CuCr₂O₄ spinel were greatly influenced by the annealing temperature. The as-burnt powder and CuCr₂O₄ spinel ceramic pigment were then employed to fabricate thickness sensitive spectrally selective (TSSS) paint coatings by a convenient spray-coating technique. The results revealed that spectral selectivity of TSSS paint coatings based on CuCr₂O₄ spinel ceramic pigments was much better than that of paint coatings based on the as-burnt powders. Furthermore, the effect of surface features of TSSS paint coatings on its optical property and hydrophobicity was investigated in detailed.