Three inorganic–organic hybrid framework cadmium thiosulfate phases have been investigated for adsorption and photodegradation of organic dye molecules. Different classes of organic dyes, viz., triaryl methane, azo, xanthene, anthraquinone, have been studied. The anionic dyes with sulfonate groups appear to readily adsorb on the cadmium thiosulfate compounds in an aqueous medium. The adsorption of the dye molecules, however, does not create any structural changes on the cadmium thiosulfate compounds, though weak electronic interactions have been observed. The adsorbed dyes have been desorbed partially in an alcoholic medium, suggesting possible applications in scavenging specific anionic dyes from the aqueous solutions. Langmuir adsorption/desorption isotherms have been used to model this behavior. UV-assisted (λ_max = 365 nm) photocatalytic decomposition studies on the cationic dyes indicate reasonable activity comparable with that of Degussa P-25 (TiO₂) catalyst. Sunlight assisted photocatalytic studies have been carried out in detail employing hybrid framework compounds. The Langmuir–Hinshelwood kinetics model, employed to follow the degradation profile of the organic dyes, indicates that the photocatalytic degradation follows the order: triaryl methane > azo > xanthene.