This study explores the development of TiO₂/perovskite (CsPbBr₃) S-scheme heterojunctions for efficient CO₂ photoreduction into solar fuels. The heterojunctions are synthesized through a facile electrostatic-driven self-assembling approach, combining TiO₂ nanofibers with CsPbBr₃ quantum dots (QDs). Density functional theory (DFT) calculations and experimental studies confirm the electron transfer from CsPbBr₃ QDs to TiO₂, creating an internal electric field (IEF) that directs electrons from TiO₂ to CsPbBr₃ upon light irradiation. This IEF facilitates the separation of electron-hole pairs, enhancing the photocatalytic activity. The resulting TiO₂/CsPbBr₃ nanohybrids 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 labeling experiments confirm that the reduction products originate from CO₂. The work provides a novel approach to designing efficient photocatalysts for CO₂ photoreduction.This study explores the development of TiO₂/perovskite (CsPbBr₃) S-scheme heterojunctions for efficient CO₂ photoreduction into solar fuels. The heterojunctions are synthesized through a facile electrostatic-driven self-assembling approach, combining TiO₂ nanofibers with CsPbBr₃ quantum dots (QDs). Density functional theory (DFT) calculations and experimental studies confirm the electron transfer from CsPbBr₃ QDs to TiO₂, creating an internal electric field (IEF) that directs electrons from TiO₂ to CsPbBr₃ upon light irradiation. This IEF facilitates the separation of electron-hole pairs, enhancing the photocatalytic activity. The resulting TiO₂/CsPbBr₃ nanohybrids 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 labeling experiments confirm that the reduction products originate from CO₂. The work provides a novel approach to designing efficient photocatalysts for CO₂ photoreduction.