The redox-neutral Fe-electrocatalytic deoxygenative Giese reaction elucidated herein represents a powerful approach for the one-step installation of Michael acceptors into both primary and secondary alcohols. The key feature of this reaction is its independence from scarce metals or highly toxic reagents, allowing the use of readily available commercial reagents to effortlessly form C-C bonds from alcohols at ambient temperature. In addition, the previously unreported achievement of cathodic reduction, which facilitates the electrochemical reduction of the Fe-catalyst, has been realized. Coupled with the Appel reaction via anodic oxidation, a redox-neutral Giese reaction was achieved, providing tremendous efficiency for small molecule diversification. This methodology represents a pioneering investigation into the fusion of Fe-catalysis and electrochemistry in the field of redox-neutral reactions. In the near future, the exploration of diverse innovative reactions utilizing this redox cycle holds promising prospects. In addition, the application of this approach in the field of medicinal chemistry is expected to further advances in medicinal chemistry.