This study presents a unique S-scheme heterojunction in self-assembled TiO₂/CsPbBr₃ hybrids for efficient CO₂ photoreduction. The heterojunction is synthesized via an electrostatic-driven self-assembly method, resulting in an internal electric field (IEF) that facilitates efficient charge separation. Density functional theory (DFT) calculations and experimental studies confirm that electrons transfer from CsPbBr₃ quantum dots (QDs) to TiO₂, creating an IEF that directs photoexcited electrons from CsPbBr₃ to TiO₂ upon light irradiation. This S-scheme heterojunction significantly enhances the separation of electron-hole pairs, promoting efficient CO₂ photoreduction. The hybrid nanofibers exhibit a higher CO₂ reduction rate (9.02 μmol g⁻¹ h⁻¹) compared to pristine TiO₂ nanofibers (4.68 μmol g⁻¹ h⁻¹). Isotope tracer results confirm that the reduction products originate from CO₂. The study highlights the potential of TiO₂-based photocatalysts with S-scheme heterojunctions for efficient CO₂ photoreduction. The results demonstrate that the S-scheme charge transfer pathway enhances the redox ability of electrons in CsPbBr₃ and holes in TiO₂, leading to improved CO₂ reduction performance. The work provides insights into the design of photocatalysts with distinct heterojunctions for efficient CO₂ reduction.This study presents a unique S-scheme heterojunction in self-assembled TiO₂/CsPbBr₃ hybrids for efficient CO₂ photoreduction. The heterojunction is synthesized via an electrostatic-driven self-assembly method, resulting in an internal electric field (IEF) that facilitates efficient charge separation. Density functional theory (DFT) calculations and experimental studies confirm that electrons transfer from CsPbBr₃ quantum dots (QDs) to TiO₂, creating an IEF that directs photoexcited electrons from CsPbBr₃ to TiO₂ upon light irradiation. This S-scheme heterojunction significantly enhances the separation of electron-hole pairs, promoting efficient CO₂ photoreduction. The hybrid nanofibers exhibit a higher CO₂ reduction rate (9.02 μmol g⁻¹ h⁻¹) compared to pristine TiO₂ nanofibers (4.68 μmol g⁻¹ h⁻¹). Isotope tracer results confirm that the reduction products originate from CO₂. The study highlights the potential of TiO₂-based photocatalysts with S-scheme heterojunctions for efficient CO₂ photoreduction. The results demonstrate that the S-scheme charge transfer pathway enhances the redox ability of electrons in CsPbBr₃ and holes in TiO₂, leading to improved CO₂ reduction performance. The work provides insights into the design of photocatalysts with distinct heterojunctions for efficient CO₂ reduction.