In the current exploration, a sequence of AlP1-xVxO4 (x = 0, 0.05, 0.1, 0.15, 0.2) inorganic pigments were synthesised by chemical precipitation method using K3PO4 as a self-precipitation agent. Higher loading of vanadium (x = 0.15) into the P5+ lattice changed the crystal structure from tridymite (x = 0–0.1) to crystobolite which is supported by Powder X-ray diffraction analysis. Strain in the lattice was observed due to the substitution of higher ionic radii V5+ (0.35 Å) element, in the lower ionic radii P5+ (0.17 Å) framework. A drastic shift in the absorption curve to a higher wavelength was observed due to the insertion of vanadium in the AlPO4 system. A steady increase in the yellow hue was observed as a result of the substitution effect and the charge transfer transition occurred between V5+ and O2−. Though serious agglomerations of particles are noticed in the SEM and TEM micrographs, spherical shape particles are noticed after careful analysis of TEM images. The NIR reflectance of all the fabricated materials is found to be R > 75% and the chemical stability test confirmed all the recipes are stable (<2% weight loss and color change) in the harsh chemical conditions proving the materials can be used for metallic coating applications.