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[Display omitted] • Successfully designed and prepared heterojunction V o/BiVO 4 -TiO 2. • Reveal the mechanism of oxygen vacancies improving photocatalytic performance. • Elucidate the electron transfer pathways at V o/BiVO 4 -TiO 2 interfaces. Constructing heterojunction photocatalysts is a promising way to efficiently degrade organic pollutants, while its application is constrained by slow interfacial dynamics. Reported herein is an easy strategy to construct S-scheme heterojunction between BiVO 4 with oxygen vacancies (V O) and TiO 2. The V o/BiVO 4 -TiO 2 heterojunction exhibited excellent efficiency in degrading Levofloxacin (LVFX) (99.21 % degradation within 90 min) and significantly enhanced degradation kinetic (4.03 × 10-2min−1), which was 2.6 times than BiVO 4 -TiO 2 (1.53 × 10-2min−1). The mechanism lies in the fact that the introduction of V O into BiVO 4 produces impurity bands that reduce its work function, which increases the difference in Fermi energy levels of the heterojunction and, in turn, enhances the Interfacial Electric Field. Based on the experimental and theoretical simulations results, the charge transfer path at the interface of V o/BiVO 4 -TiO 2 was elucidate. This work reveals the microscopic mechanism of electric field enhancement at heterojunction interface and provides new insights for designing efficient heterojunction photocatalysts. [ABSTRACT FROM AUTHOR]