The oxidative esterification of various aldehydes with alcohols could be achieved by a heterogeneous iron(III) catalyst supported on a ring-like POM inorganic ligand under mild conditions, affording the corresponding esters, including several drug molecules and natural products, in high yields. ESI-MS and control experiments demonstrated that POM-Fe^V(O) was the active catalytic species and the plausible mechanism was presented. More importantly, the 6th run of the iron catalyst recycles shows only a slight decrease in the yield.