Complex inorganic green pigments having a high near infrared solar reflectance have been synthesized. Cr₂O₃ is the host component and mixtures of TiO₂, Al₂O₃, and V₂O₅ were used as the guest components. TiO₂, Al₂O₃ and V₂O₅ were mixed into 39 different compositions. It was found that a sample, denoted by S9, with a composition of Cr₂O₃, TiO₂, Al₂O₃ and V₂O₅ of 80, 4, 14 and 2 wt% respectively, gives a maximum near infrared solar reflectance of 82.8%. The S9 pigment powder was then prepared as a reflective coating material with different amounts of pigment powder from 4–8 g in 100 g of ceramic glaze. The prepared materials were sprayed on the clay tiles for reflectance measurements. It was found that 6 g of S9 pigment powder mixed with 100 g of ceramic glaze gives the highest near-infrared reflectance value of 74.5%. The newly synthesized pigment is a suitable ceramic roof coating for its high reflectance performance and the durability performing once the ceramic roof installed on house.