In this work, we reported obtaining mesoporous Bi-doped TiO2 by mechanosynthesis and bismuth loading of 0%, 1%, 3%, 5%, and 10% (milled TiO2, TiO2 Bi 1%, TiO2 Bi 3% TiO2 Bi 5%, and TiO2 Bi 10%, respectively). The effect of bismuth doping and ball milling on the crystal structure, optical properties, and photocatalytic performance of Bi-doped TiO2 mesoporous samples under UV, visible, and sun irradiation was investigated. According to the results of the Rietveld refinement, the estimated chemical formulas for the TiO2 Bi 1%, TiO2 Bi 3%, TiO2 Bi 5%, and TiO2 Bi10% samples were Ti0.99Bi0.01O2, Ti0.97Bi0.03O2, Ti0.96Bi0.04O2, and Ti0.91Bi0.09O2 respectively. The incorporation of Bi into the TiO2 lattice causes the crystallite size to decrease and, consequently, the absorption spectrum of TiO2 to extend into the visible region of the electromagnetic spectrum, resulting in a lower band gap (Eg) value. Bi-doped TiO2 mesoporous samples had Eg values of 2.90 eV, 2.83 eV, 2.77 eV, and 2.70 eV for the TiO2 Bi 1%, TiO2 Bi 3%, TiO2 Bi 5%, and TiO2 Bi 10% samples, respectively. Photocatalytic removal of methylene blue (MB) data fit well for second-order kinetics. Photocatalytic activity increase followed the order of TiO2 Bi 5% > TiO2 Bi 10% > TiO2 Bi 3% > TiO2 Bi 1% > pristine TiO2. The TiO2 Bi 5% sample exhibited excellent photocatalytic performance for MB photodegradation under natural sunlight (89.2%).