Bismuth vanadate-based pigments deposited on marshalite are synthesized by the low-temperature combustion reaction method using vanadium oxide V2O5 and bismuth salt BiONO3·H2O. The quantitative composition of the starting components is calculated from the BiVO4 -to- marshalite ratio = 1:3. To clarify the pigment, zinc nitrate Zn(NO3)2·6H2O and calcium hydroxide Ca(OH)2 are added. Citric acid is used as an energetic and gas-forming additive. X-ray diffraction analysis (DRON-3M diffractometer, filtered CuKα radiation) showed the formation of a microimpurity such as VO2 oxide during the synthesis of bismuth vanadate. The phase of the complex Aurivillius-type oxide Bi4V2011 that gives the pigments a beige tint is found along with bismuth vanadate and marshallite during the synthesis of the pigment on a mineral substrate (marshallite). IR spectroscopic analysis (Nicolet 5700 IR Fourier spectrometer) showed that the fixation of bismuth vanadate-based pigment was caused by silanol groups located on the surface of marshalite and the incorporation of VO4 tetrahedra into the surface of marshalite due to the formation of “umbrella-shaped” bonds (Si-O-V). The absorption bands at 1370,2 cm −1 , 1397.0 cm −1 , and 1757.7 cm −1 indicate the presence of carbonate groups on the surface of the pigment, related to both chemisorbed carbon dioxide CO2 and carbonate ion CO3 2- . The dispersion of pigment is determined by the dispersion of marshalite, which acts as a mineral substrate. The pigment is stable up to 750°C; an increase in the treatment temperature leads to its darkening.