Reported here, inorganic molecular tetrairon(III)-substituted polyoxotungstate [FeIII4(H2O)2(P2W15O56)2]12− is firstly used to catalyze visible-light-driven oxygen evolution, which displays excellent catalytic activity (O2 yield of 48%, turnover number (TONcatalyst) of 900 and quantum (ΦQY) yield of 24%) in a homogeneous system. The O2 yield and TON of Fe4POM catalyst rank third and fourth among thirty documented homogeneous photocatalytic water oxidation catalysts based on POMs, respectively. In order to recover and reuse the homogeneous catalysts, it is realistic and necessary to heterogenize the homogeneous molecular catalyst. The electrostatic interaction is rationally designed as solid connection between ((3-aminopropyl)triethoxysilane) apts-modified mesoporous SBA-15 and polyoxoanion (Fe4POM). The catalytically active species of immobilized polyoxometalate maintains intact before and after the photocatalytic water oxidation, which is adequately confirmed by various spectroscopic techniques such as solid phosphorus-31 nuclear magnetic resonance spectra (31P MAS NMR), X-ray photoelectron spectra (XPS) and transmission electron microscopy (TEM) images.