TiO2 nanotube arrays sensitized with Sb2S3 microcrystalline were successfully fabricated by a two-step process of photodeposition method followed by annealing treatment. The structural investigation by X-ray diffraction, scanning electron microscopy and transmission electron microscopy indicated that the Sb2S3 microparticles grew uniformly on the walls of TiO2 nanotubes. The amorphous Sb2S3 microspheres could be transformed into octahedral microcrystals after annealing treatment. The Sb2S3 modification of the TiO2 nanotube arrays resulted in an increase in visible light adsorption and photocatalytic activities toward degradation of methyl orange (MO) and rhodamine B (RhB) dyes under visible light irradiation.