We report a low cost and environmentally-friendly solvent system to synthesize TiO2 nanoparticles using an acidic deep eutectic solvent, choline chloride/p-toluene sulphonic acid as a templating and hydrolyzing agent via sol–gel method. The effect of varying concentration of the deep eutectic solvent (DES) on the important physico-chemical characteristics of as-synthesized TiO2 such as phase, morphology, particle size, surface area and band gap energy was studied. A detailed characterization of the obtained nanomaterials has been performed using various techniques, including X-ray diffraction (XRD), Scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area, Raman and Ultraviolet–visible absorption spectroscopy. The spherical TiO2 nanoparticles were found to be biphasic with two phases: anatase and rutile having crystallite sizes in the range of 5.6–6.8 nm. These nanoparticles assembled together to form a coral-like morphology. The effect of calcination temperature on the synthesized products was studied by heating at 750 °C. The photocatalytic activity of the prepared TiO2 materials was evaluated by the photo-discoloration of an aqueous methyl orange dye solution (20 ppm) under UV light irradiation. The results indicate that the photocatalytic efficiency of an anatase–rutile mixture in the optimal sample DES-3 is higher (98% within 3 h) than a commercially available Degussa P-25 (87% within 3 h).