Toluene is an extensively used reagent that could cause water pollution and endanger human health. In this work, an O3/UV/ion-doped TiO2 nanotubes process was investigated to obtain the optimum TiO2 nanotubes for effective toluene decomposition. Photocatalytic activity is found to be influenced by the doped-ion type by affecting the ionic radius, valence state, and configuration of the dopant. The calcination temperature and doping concentration, which change the weight fractions of the anatase phase (fA), the Brunauer-Emmett-Teller surface area (SBET), and the energy band gap (Eg) of the catalyst, also affect the photocatalytic activity. When TiO2 is doped with ions, SBET decreases and Eg becomes narrower. The photocatalytic activities of TiO2 for toluene removal increase after doping with Ag(+), Al(3+), Cu(2+), Fe(3+), Mn(2+), Ni(2+), V(5+), and Zn(2+). Moreover, the 1.0% Fe(3+)-doped TiO2 nanotubes calcined at 550 °C have the highest catalytic activity, with a toluene removal efficiency of 70.7%.