A novel near-infrared reflecting inorganic pigments Fe/N co-doped MgTiO3 have been prepared by the Sol-Gel method. Fe/N co-doped MgTiO3 displays wide range of colors from white to red-brown. The pigments possess high NIR solar reflectance (>53.51%). Indoor air temperature difference of boxes in the simulation test reaches 2.0–3.0 °C. The interior surface temperature difference of the two pigmented coatings is above 2.4 °C.