A high NIR-reflective black pigment is developed by Mn doping of Fe2O3. The pigment powders are prepared by spray pyrolysis, and the effect of the Mn concentration on the blackness and optical properties is investigated. Mn doping into the crystal lattice of -Fe2O3 is found to effectively change the powder color from red to black, lowering the NIR reflectance compared to that of pure Fe2O3. The pigment doped with 10% Mn, i.e., Fe1.8Mn0.2O3, exhibits a black color with an optical bandgap of 1.3 eV and a Chroma value of 1.14. The NIR reflectance of the prepared Fe1.8Mn0.2O3 black pigment is 2.2 times higher than that of commercially available carbon black, and this material is proven to effectively work as a cool pigment in a temperature rise experiment under near-infrared illumination.