Tungsten oxide (WO₃) nanomaterials have become a hot spot in the current research on metal oxides due to their good antibacterial and anticancer properties. In this paper, WO₃ was prepared by the sol–gel method, and samples with different structures and morphologies were obtained by controlling the pH value. Ammonium paratungstate and tetrabutyl titanate were used as raw materials, and the amount of Tetrabutyl titanate (TBOT) was changed to regulate the TiO₂/WO₃ samples were prepared by varying the amount of TBOT. The structure, morphology and luminescence properties were also investigated. The results show that the monoclinic WO₃ nanoparticles as well as TiO₂/WO₃ composite nanomaterials were prepared successfully. Under acidic and alkaline conditions, the particles are mainly rod-shaped and granular, and the smaller the pH is, the smaller the particle size is. The average grain size is 49.8 nm. The strongest luminescence of the samples at 611 nm was evident at an excitation wavelength of 394 nm. The luminescence property of WO₃ prepared under alkaline condition is better than that under acidic condition. The luminescence intensity of the prepared TiO₂/WO₃ composites by adding 1 ml TBOT in acidic conditions increased by 21% compared with that of 2 ml TBOT. The luminescence intensity of the prepared TiO₂/WO₃ composites by adding 2 mL TBOT in alkaline condition increased by 14% compared with that prepared by adding 1 mL TBOT.