In this study, the electronic and photocatalytic properties of core-shell heterojunctions photocatalysts with reversible configuration of TiO₂ and Bi₂O₃ layers were studied. The core-shell nanostructure, obtained by efficient control of the sol-gel polymerization and impregnation method of variable precursors of semiconductors, makes it possible to study selectively the role of the interfacial charge transfer in each configuration. The morphological, optical, and chemical composition of the core-shell nanostructures were characterized by high-resolution transmission electron microscopy, UV-visible spectroscopy and X-ray photoelectron spectroscopy. The results show the formation of homogenous TiO₂ anatase and Bi₂O₃ layers with a thickness of around 10 and 8 nm, respectively. The interfacial charge carrier dynamic was tracked using time resolved microwave conductivity and transition photocurrent density. The charge transfer, their density, and lifetime were found to rely on the layout layers in the core-shell nanostructure. In optimal core-shell design, Bi₂O₃ collects holes from TiO₂, leaving electrons free to react and increase by 5 times the photocatalytic efficiency toward H₂ generation. This study provides new insight into the importance of the design and elaboration of optimal heterojunction based on the photocatalyst system to improve the photocatalytic activity.