Multiphase photocatalysts Cd1−xZnxS/TiO2 were synthesized through the deposition of solid solutions of cadmium and zinc sulfides on the surface of titania samples with different porous structures, including a 3D‐ordered meso/macroporous structure. The photocatalysts were characterized by a wide range of experimental techniques: X‐ray diffraction, high‐resolution transmission electron microscopy combined with energy‐dispersive X‐ray spectroscopy, N2 adsorption at 77 K, X‐ray photoelectron spectroscopy, and UV/VIS spectroscopy. The photocatalytic activity was tested in a batch reactor for the H2 evolution reaction from aqueous solutions of Na2S/Na2SO3 under visible‐light irradiation (λ=450 nm). The highest achieved photocatalytic activity was 1.8 mmol H2 per gram of photocatalyst per hour. The regular porous structure of titania was demonstrated to enhance the photocatalytic activity and stability of Cd0.4Zn0.6S/TiO2 samples.