In artificial photocatalysis, sluggish kinetics of hole transfer and the high recombination rate of charge have been the Achilles' heel of photocatalytic conversion efficiency. The development of co-catalysts for promoting exciton splitting and charge separation has therefore gained continuous attention. Herein, "Co4O4" cubane complex Co4O4(O2CMe)(4)(PY)(4) (1a, py = pyridine derivatives), serves as a homogeneous molecular co-catalyst which is engineered into the framework of pristine polymeric carbon nitride (PCN) for water oxidation with light illumination. This modification strategy maximizes the contact areas between co-catalysts and reactants, reduces the over-potential of oxygen producing and accelerates the interface transfer rate of electron-hole pairs, thus leading to enhanced reaction kinetics for photocatalytic water oxidation. Compared with pristine PCN, the photocatalytic O-2 production rate up to 19-fold-enhanced in the presence of molecular co-catalyst. This work emphasizes the importance of developing effective, stable and earth-abundant molecular co-catalysts for the promotion of water-splitting photocatalysis.