This study presents an efficient S-scheme heterojunction composed of In₂O₃ and Nb₂O₅, which enables ultrafast electron transfer for CO₂ photoreduction. The heterojunction is fabricated via a one-step electrospinning method, resulting in intimate contact between the two phases and facilitating rapid interfacial electron transfer (<10 ps). This ultrafast transfer enhances the separation of photoelectrons and holes, leading to extended lifetimes and improved participation in subsequent photoreactions. The Nb₂O₅ component is effective in chemisorbing and activating CO₂ molecules, contributing to enhanced CO₂ conversion performance. The S-scheme heterojunction structure allows for efficient charge separation and transfer, which is crucial for the photocatalytic reduction of CO₂. The study also demonstrates that the hybrid nanofibers exhibit high stability and recyclability, with minimal decline in performance over multiple cycles. The results highlight the importance of interfacial contact in achieving efficient charge transfer and the potential of S-scheme heterojunctions in photocatalytic CO₂ reduction. The findings provide insights into the role of ultrafast charge transfer in enhancing the efficiency of CO₂ photoreduction.This study presents an efficient S-scheme heterojunction composed of In₂O₃ and Nb₂O₅, which enables ultrafast electron transfer for CO₂ photoreduction. The heterojunction is fabricated via a one-step electrospinning method, resulting in intimate contact between the two phases and facilitating rapid interfacial electron transfer (<10 ps). This ultrafast transfer enhances the separation of photoelectrons and holes, leading to extended lifetimes and improved participation in subsequent photoreactions. The Nb₂O₅ component is effective in chemisorbing and activating CO₂ molecules, contributing to enhanced CO₂ conversion performance. The S-scheme heterojunction structure allows for efficient charge separation and transfer, which is crucial for the photocatalytic reduction of CO₂. The study also demonstrates that the hybrid nanofibers exhibit high stability and recyclability, with minimal decline in performance over multiple cycles. The results highlight the importance of interfacial contact in achieving efficient charge transfer and the potential of S-scheme heterojunctions in photocatalytic CO₂ reduction. The findings provide insights into the role of ultrafast charge transfer in enhancing the efficiency of CO₂ photoreduction.