In this work, we fabricated boron/samarium co-doped TiO2 nanomaterials (B/Sm-TiO2) by a sol-gel method. The effects of calcination temperature on the crystal texture, grain size, and photocatalytic characteristics were investigated by XRD, XPS, SEM, TEM, and UV–vis DRS. Using the Materials Studio software and density functional theory, the band structures and state densities of TiO2 single or codoped B and Sm ions have been determined. The photocatalytic degradation of methyl orange under visible light was used to evaluate the photocatalytic performance of B/Sm-TiO2 nanomaterials. The results demonstrate that the photocatalytic performance of B/Sm-TiO2 nanomaterials is significantly affected by different calcination temperatures. With the increase of calcination temperature, the size of TiO2 particles increases, and the TiO2 phase changes from anatase to rutile with a crystalline transition temperature of 700 °C. The visible light absorption of B/Sm-TiO2 under the forging condition of 600 °C is enhanced accordingly, the degradation efficiency is improved, and the degradation rate of methyl orange reaches 89% after 60 min of light irradiation.