A series of heterostructures (Fe3+/Fe2+) incorporated on SnO2/TiO2, SnO2 and TiO2 were prepared by the photochemical reduction method in neat water and 30% PriOH in water as a solvent medium and were characterized. XPS analysis confirmed the reduced state of Fe3+/Fe2+ on composite materials and introduced new additional energy level to diminish the recombination rate of photo-generated electron-hole pairs to photocatalytic reaction. The synergistic effect of SnO2/(Fe3+/Fe2+)/TiO2 composites is more efficient in pH 3, and the presence of organic sacrificial reagents like EDTA and citric acid to trap centre of holes created on the catalyst surface to degrade the Cr(VI) ion. The photocatalytic reduction of potassium dichromate is described by the pseudo-first order kinetic equation. Ternary SnO2/(Fe3+/Fe2+)/TiO2 composites were speculated to accelerate the effective separation of electron-hole (e‒/h+) pairs, and enhanced the transportation rate of ecb− to the pollutants improved the photocatalytic activity than the (Fe3+/Fe2+)/SnO2 and (Fe3+/Fe2+)/TiO2 binary components.