Ti-Al-V-doped Cr₂O₃ green pigments could present a higher near-infrared (NIR) reflectance compared to pure Cr₂O₃. The amount of Ti and V introduced in the Cr₂O₃ matrix has been systematically varied respectively, in order to evaluate the effects of Ti and V contents on the NIR properties of the doped Cr₂O₃. For comparison, experimental reflectance measurements and mean-NIR reflectance (780–2000 nm) of samples are given. The results reveal significant variations in the NIR region as a function of nominal composition for both Ti-doped Cr₂O₃ and V-doped Cr₂O₃. Moreover, the NIR reflectance of a Ti-Al-V-doped Cr₂O₃ pigment sample was measured. It has been found that it exhibits lower NIR reflectance compared to that reported in previous study. The correlations between electronic structural and spectroscopic features are discussed. For the Ti-doped Cr₂O₃ samples, the decrease of free carriers and the electronic transitions between defect energy levels within the band gap and the conduction band, could be responsible for the variable NIR reflectance. However, for V-doped Cr₂O₃, apart from light absorptions of free carriers, there are new light absorption peaks range from 1190 to 2000 nm, resulting in the variations of the NIR reflectance.