The cobalt-coordinated polyterthiophene/hematite hybrid photoanode, denoted as Co@PTTh-N/α-Fe2O3, was fabricated to facilitate the photo-driven water oxidation reaction. The optimally aligned energy levels of the PTTh-N/α-Fe2O3 heterojunction promoted charge transfer and decreased charge recombination. The phenanthroline functional groups within PTTh-N coordinated with Co2+ ions that serve as effective catalytic centers for water oxidation, resulting in a significant enhancement of photocurrent.