A new series of yellow inorganic pigments possessing high near-infrared (NIR) reflectance (91-96% at 1100 nm), based on molybdenum-doped yttrium cerate was synthesized by traditional solid-state route. The band gap of the designed pigments changes from 3.01 to 2.44 eV, displaying colors ranging from ivory-white to yellow. The coloring mechanism is attributed to the O-2p-Mo-4d charge-transfer transition. The pigments are environmentally benign and effectively confer their NIR reflectance properties to a roofing material like asbestos.