The metal-free stoichiometric click reaction between thiol-functionalized nanocrystalline starch and yne-functional oxo-vanadium Schiff base has been demonstrated to be a simple, quantitative, mild and efficient approach for the development of heterogenized homogeneous complex via covalent bonding. The developed catalyst has found to be highly efficient and recyclable for the oxidation of various alcohols to corresponding carbonyl compounds with t-BuOOH under mild reaction conditions. Importantly, no leaching of metal or ligand is observed during the course of the reaction. (C) 2013 Elsevier B.V. All rights reserved.