The objective of this work was to develop an effective technique for removing multiple component dye wastewater. Saturation Keggin-type phosphotungstic acid (H₃PW₁₂O₄₀) was introduced to prepare TiO₂/H₃PW₁₂O₄₀ film for photocatalytic degradation of four monocomponent dye wastewater as rhodamine B (RhB), methyl orange (MO), malachite green (MG), and alizarin red (ARS), as well as bicomponent dye wastewater of RhB-MG with different volume ratio. The results indicated that the photocatalytic efficiency of TiO₂/H₃PW₁₂O₄₀ film toward cation dyes (98.5% RhB and 95.2% MG) was higher than that of anion dyes (89.8% ARS and 48.8% MO) after 240 min solar-like irradiation, during which the adsorption acted as the controlling process, whereas in the bicomponent dye solution of RhB-MG, the degradation RhB was restrained due to the competition for the active sites of catalyst surface with MG. This work could provide necessary information for the treatment of multiple component dye wastewater in practical applications.