The Cu+ active sites have gained great attention in electrochemical nitrate reduction, offering a highly promising method for nitrate removal from water bodies. However, challenges arise from the instability of the Cu+ state and microscopic structure over prolonged operation, limiting the selectivity and durability of Cu+-based electrodes. Herein, a self-reconstructed Cu2O/TiO2 nanofibers (Cu2O/TiO2 NFs) catalyst, demonstrating exceptional stability over 50 cycles (12 h per cycle), a high NO3 --N removal rate of 90.2%, and N2 selectivity of 98.7% is reported. The in situ electrochemical reduction contributes to the self-reconstruction of Cu2O/TiO2 nanofibers with stabilized Cu+ sites via the electronic metal-support interaction between TiO2 substrates, as evidenced by in situ characterizations and theoretical simulations. Additionally, density functional theory (DFT) calculations also indicate that the well-retained Cu+ sites enhance catalytic capability by inhibiting the hydrogen evolution reaction and optimizing the binding energy of *NO on the Cu2O/TiO2 NFs heterostructure surface. This work proposes an effective strategy for preserving low-valence-state Cu-based catalysts with high intrinsic activity for nitrate reduction reaction (NO3RR), thereby advancing the prospects for sustainable nitrate remediation technologies.