TiO2 used for photocatalytic water purification is most active in the form of nanoparticles (NP), but their use is fraught with difficulties in separation from solution or/and a tendency to agglomerate. The novel materials designed in this work circumvent these problems by immobilizing TiO2 NPs on the surface of exfoliated clay minerals. A series of TiO2/clay mineral composites were obtained using five different clay components: the Na-, CTA-, or H-form of montmorillonite (Mt) and Na- or CTA-form of laponite (Lap). The TiO2 component was prepared using the inverse microemulsion method. The composites were characterized with X-ray diffraction, scanning/transmission electron microscopy/energy dispersive X-ray spectroscopy, FTIR spectroscopy, thermal analysis, and N2 adsorption–desorption isotherms. It was shown that upon composite synthesis, the Mt interlayer became filled by a mixture of CTA+ and hydronium ions, regardless of the nature of the parent clay, while the structure of Lap underwent partial destruction. The composites displayed high specific surface area and uniform mesoporosity determined by the size of the TiO2 nanoparticles. The best textural parameters were shown by composites containing clay components whose structure was partially destroyed; for instance, Ti/CTA-Lap had a specific surface area of 420 m2g−1 and a pore volume of 0.653 cm3g−1. The materials were tested in the photodegradation of methyl orange and humic acid upon UV irradiation. The photocatalytic activity could be correlated with the development of textural properties. In both reactions, the performance of the most photoactive composites surpassed that of the reference commercial P25 titania.