A facile wet chemical approach has been devised for the preparation of self-assembled, high surface area, nanostructured Mn2O3 through an effective polymer-surfactant interaction. Its outstanding catalytic property for the selective transformation of alcohols to aldehydes has been reported. The polyethylene glycol/sodium dodecyl sulphate conjugates act as soft templates for the formation of manganese oxide nanorods upon treatment of a weak base, namely, diethanolamine, with manganese acetate as a precursor under mild refluxing conditions. The Mn2O3 nanorods were found to be efficient and selective catalysts for the synthesis of valuable aldehydes and ketones over undesirable acid by-products using a low catalyst loading. The precursor alcohols bearing activated and unactivated aromatic rings, double and triple bonds, and chiral sugar moiety were tolerated in this direct oxidative transformation strategy developed under benign reaction conditions.