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Although the electrochemical CO2 reduction (CO2RR) to formic acid (HCOOH) is universally governed by the *OCHO intermediate, we demonstrate that a built-in electric field at a conventionally fabricated Cu2O–Bi2O3 interface fundamentally reverses this pathway via a field-controlled microenvironment reconstruction (FCMR) mechanism. The FCMR process selectively stabilizes the *OCOH intermediate, and the addition of an ionic liquid further amplifies this shift by fine-tuning the interfacial environment. The resulting catalyst achieves >95% Faradaic efficiency for HCOOH over 140 h in an H-cell and maintains >91% efficiency at 350 mA cm–2 for 24 h without carbonate precipitation in a flow cell. This work establishes a general design principle: steering reaction pathways in composite catalysts via interfacial electric field control, thereby overcoming the thermodynamic constraints of traditional intermediates.