The construction of a potential heterojunction catalyst with proper interface alignment has become a hot topic in the scientific community to effectively utilize solar energy. In this work, a one-dimensional TiO2 nanofiber/BiOBr S-scheme heterojunction was synthesized, and charge carrier dynamics within the interface channel were explored. In addition, we incorporated mixed phase TiO2 with point defects and oxygen vacancies, which greatly promoted the initial band edge shift from the UV region. Upon the addition of BiOBr, absorption in the visible light region of the electromagnetic (EM) spectrum was observed with a decrease in the optical band gap value. The optimized BiOBr heterojunction (BTNF1.5) revealed a higher photocatalytic RhB dye degradation efficiency due to the efficient generation and separation of charge carriers upon light irradiation. The optimum sample BTNF1.5 showed a high degradation efficiency of 98.4% with a rate constant of 47.1 min-1 at 8 min of visible light irradiation, which is double than that of the pure TiO2. Electrochemical analysis, time-resolved photoluminescence and Kelvin probe measurement revealed an S-scheme charge-transfer mechanism within the BiOBr/TiO2 system. This work provides a strategy for the facile synthesis of heterojunction photocatalysts exhibiting exceptional catalytic performance.