The charge transfer is a key issue in the development of efficient photoelectrodes. Here, we report a method using F-doping and dual-layer ultrathin amorphous FeOOH/CoOOH cocatalysts coupling to enable the inactive α-FeO photoanode to become highly vibrant for the oxygen evolution reaction (OER). Fluorine doping is revealed to increase the charge density and improve the conductivity of α-FeO for rapid charge transfer. Furthermore, ultrathin FeOOH was deposited on F-FeO to extract photogenerated holes and passivate the surface states for accelerated charge carrier transfer. Moreover, CoOOH as an excellent cocatalyst was coated onto FeOOH/F-FeO with the photoassisted electrodeposition method remarkably expediting OER kinetics through an optional pathway of holes utilized by Co species. Ultimately, the CoOOH/FeOOH/F-FeO photoanode exhibits a satisfactory photocurrent density (3.3-fold higher than pristine α-FeO) and a negatively shifted onset potential of 80 mV. This work showcases an appealing maneuver to activate the water oxidation performance of the α-FeO photoanode by an integration strategy of heteroatom doping and cocatalyst coupling.