Chitosan-montmorillonite (CS-MT) composites of different MT composition were prepared in 5% of acetic acid solution and fabricated on glass plates. The composite film was then combined with TiO2 in an immobilized layer-layer manner for removing methyl orange dye via synergistic photocatalytic-adsorption processes. The effects of MT addition to the CS matrix were investigated with respect to the physicochemical and optical properties. The presence of MT within the composite reduced the swelling and improved the adhesiveness as well as the thermal stability of CS. The MT clay assisted in producing higher hydroxyl radicals and improving the solid-state oxidation of CS within the adsorbent sub-layer for the photocatalytic enhancement of TiO2/CS-MT than its counterpart TiO2/CS. Subsequently, the photocatalytic activity of the TiO2/CS-MT was 1.3 and 4.2-times better than the TiO2/CS and TiO2 photocatalysts, respectively. This TiO2/CS-MT photocatalyst was also reusable for at least ten cycles of application.