Clinobisvanite (monoclinic scheelite BiVO4,S.G.I2/b) has garnered interest as a wide-band semiconductor with photocatalyst activity, as a high NIR reflectance material for camouflage and cool pigments and as a photoanode for PEC application from seawater. BiVO4exists in four polymorphs: orthorhombic, zircon-tetragonal, monoclinic, and scheelite-tetragonal structures. In these crystal structures, V is coordinated by four O atoms in tetrahedral coordination and each Bi is coordinated to eight O atoms from eight different VO4tetrahedral units. The synthesis and characterization of doped bismuth vanadate with Ca and Cr are studied using gel methods (coprecipitated and citrate metal–organic gels), which are compared with the ceramic route by means of the UV–vis–NIR spectroscopy of diffuse reflectance studies, band gap measurement, photocatalytic activity on Orange II and its relation with the chemical crystallography analyzed by the XRD, SEM-EDX and TEM-SAD techniques. The preparation of bismuth vanadate-based materials doped with calcium or chromium with various functionalities is addressed (a) as pigments for paints and for glazes in the chrome samples, with a color gradation from turquoise to black, depending on whether the synthesis is by the conventional ceramic route or by means of citrate gels, respectively; (b) with high NIR reflectance values that make them suitable as fresh pigments, to refresh the walls or roofs of buildings colored with them; and (c) with photocatalytic activity.