A novel nanocomposite material made of two-dimensional BiOCl nanoplates assembled into highly porous titania has been successfully prepared following a facile sol-gel reaction. Both the TiO2 (anatase) and BiOCl components are crystalline as demonstrated by X-ray diffraction and transmission electron microscopy analyses. TiO2 exhibits a highly porous network and possesses a small crystallite size, whereas BiOCl forms micrometer-sized plates with nanometer thicknesses. Aqueous photocatalytic activity tests with this novel material have been performed on photodegradation of Rhodamine B under ultraviolet-visible light irradiation. Interestingly, the attachment of the BiOCl nanoplates to the TiO2 network significantly enhances the photocatalytic activity of the material compared to that of pure TiO2 due to the formation of BiOCl/TiO2 heterojunctions. Thus, this pertinent synergistic combination of TiO2 and BiOCl proves to be a promising strategy for the large-scale production of a new generation of photocatalysts with excellent properties for the degradation of organic pollutants.