The present work is focused on the development of a novel flocculant for selective flocculation of iron ore using functionalized β‐cyclodextrin (β CD). β CD has been modified by esterification reaction with methacrylic anhydride (MAh) to form β CD methacrylate (CD‐Meth). After that, a three‐dimensional polymeric network structure has been prepared by free radical polymerization of CD‐Meth with copolymeric chain of poly (acrylamide‐co‐acrylic acid) through grafting. The synthesized material has been characterized in detail. It has been found that the developed material has promising selectivity toward the hematite particles and also demonstrates faster settling of hematite particles. The developed material is found to be superior in all aspects than that of conventional selective flocculant used for iron ore beneficiation (i.e., starch).