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 α-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., Fe_1.8Mn_0.2O₃, 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 Fe_1.8Mn_0.2O₃ 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.