Pollution remains one of the most significant global challenges. Photocatalysis consists of a new organic pollutant removal technology, with TiO2 widely studied as a photocatalyst in the photocatalytic removal of water pollution. However, intrinsic TiO2 has the disadvantages of weak visible light absorption, low electron separation, and transmission efficiency, as well as few active sites. In this study, anatase-phase Ti3+ self-doped TiO2 (B-TiO2) with a core-shell structure was successfully prepared by forming an amorphous layer rich in oxygen vacancies (OVs) and Ti3+ defects on the TiO2 surface under a nitrogen atmosphere using NaBH4 as a chemical-reducing agent. The visible light absorption performance of the catalyst was notably improved when exposed to light irradiation. The bending of surface energy bands facilitated the separation of photogenerated electron-hole pairs, and the core-shell structure allowed the electron-hole pairs to be transported to the surface of the catalyst and participate in the reaction faster. We observed that 92.86% of Rhodamine B (RhB) was degraded in only 5 min, an increase of 2.73 times that of the degradation rate observed in commercial P25. With extraordinary stability, the photocatalytic efficiency of the catalyst remained at 96.2% after five degradation cycles.