Anatase TiO2/SiO2 nanocomposites were prepared by a sol–gel process at a low temperature. The structural properties of these as-prepared nanocomposites were characterized with scanning electron microscopy (SEM) and X-ray diffraction (XRD), showing that TiO2 nanoparticles were deposited on the surface of SiO2 spheres. The spherical TiO2/SiO2 nanocomposites were coated onto cotton fabrics by a simple dip-pad–dry-cure process. The treated cotton fabrics demonstrated higher photocatalytic activity in comparison to pure TiO2 treated cotton fabrics in a typical photocatalytic test using a model compound of Neolan Blue 2G dye. Our results demonstrate that this composite material is a step towards better self-cleaning performance of textile materials.