© 2022, Iranian Chemical Society.TiO2 has been structured in heterojunctions with BiVO4 to amplify the photocatalytic activity under visible light irradiation. In this context, TiO2/BiVO4 nanofibers have been synthesized by combining the sol–gel chemistry and electrospinning method, and addressed for structural, morphological, optical, and degradation of indigo dye under visible illumination. Spectrophotometer studies showed that the light absorption range of TiO2 can be extended to the visible light region with the contribution of BiVO4. Visible light photocatalytic activities of the nanofiber were determined by the degradation studies of indigo dye. TiO2/BiVO4 nanofibers with 8 ratios by molar offered up to 95% degradation of the indigo dye under visible light. 8% TiO2/BiVO4 nanofiber exhibited the fastest degradation rate (0.19924 min−1), which was 7 times faster than pure TiO2 photocatalyst (0.0278 min−1). Furthermore, the recombination rate and mobility of charge carriers were characterized utilizing photoluminescence (PL) and photoelectrochemical measurements. The results were shown that the photocurrent density of TiO2/BiVO4 hybrid nanofibers was much better than that of pure BiVO4 across the visible light spectrum.