A photocatalytically active layer composed of TiO2 (Evonik P25) was successfully deposited on the macroporous (3 µm pore size) permeate side of an asymmetric porous alumina membrane with the aid of a smectite (a synthetic hectorite, Sumecton SWF) by dipping the membranes into an aqueous suspension containing P25 and the smectite. After the heat treatment at 400 °C, the coated hybrid was adhered on the macroporous support enough to be applied for the photocatalytic decomposition of organics (methylene blue and phenol as model molecules) in water. The water permeance of the membranes after the coating with the P25-smectite hybrid was reduced by only 24% compared with that of the pristine membrane, showing that the advantages of the present method for the preparation of the photocatalyst layer on the surface of the macroporous alumina without significant infiltration of the suspension into the support pores. The amount of MB and phenol degraded using the P25-SWF hybrid was equal to 0.007 and 0.023 mmol.L−1, respectively, when the reaction was carried out using the four single-channel tubular membrane reactor at transmembrane pressures of 250 mbar. The implemented photocatalytic membrane reactor can easily be up-scaled by increase the size of the membrane module, with more tubes and longer tubes (lengths up to 1 m are commercially available), paving the way to potential technological applications for the continuous treatment of polluted waters