Abstract Earth‐abundant α‐Fe 2 O 3 (hematite) is a convincing photoanode for photoelectrochemical (PEC) water splitting; however, its intrinsic properties of inferior charge transfer and sluggish water oxidation kinetics limit its performance. Here, we report a straightforward decoration method for transition metal hydroxides to accelerate the oxygen evolution reaction (OER) of hematite photoanodes grown by electric field‐assisted liquid phase deposition (EA‐LPD). The investigations revealed that Co(OH) 2 acts as a superior co‐catalyst compared with hydroxides of Mn, Fe, Co, Ni, and Zn. EA‐LPD‐grown hematite photoanode loaded with cobalt hydroxide exhibited an excellent PEC performance. A photocurrent density of 0.93 mA.cm −2 at 1.23 V versus reversible hydrogen electrode was achieved for the modified hematite, ∼3 times more than that of pristine hematite, and a cathodic shift of 100 mV for the onset potential was observed. The proposed simple and cost‐effective co‐catalyst loading strategy provides a high degree of freedom in the design of co‐catalysts with a complex chemical composition comprising transition metal oxyhydroxides and hydroxides on different photoanodes for more efficient charge carrier separation for the PEC applications.