An amorphous precursor of Cr2O3 pigment was prepared via solution combustion synthesis. After calcination at 1000 °C for 1.0 h, the precursor was converted into well-crystallized submicron Cr2O3 crystals with uniform particle distribution and low aggregation. Furthermore, Ti, Co, and Fe were doped into the lattice of Cr2O3, and the effects of these dopants on the reflectance spectroscopy modulation as well as chromatic properties were investigated in detail. As a result, a series of Cr2O3 pigment samples sharing similar spectra within the wavelength from 400 to 1600 nm with green plants could be successfully fabricated.