Polyacrylamide-grafted barley (BAR-g-PAM) was synthesized by ceric ion-based conventional method. The grafting of polyacrylamide chains on the polysaccharide backbone was confirmed through various physicochemical techniques such as intrinsic viscosity measurement, 13C-NMR spectra, FTIR spectroscopy, elemental analysis, scanning electron microscopy morphology, thermogravimetric analysis study, number-average molecular weight, and aqueous solubility. Furthermore, flocculation efficacy of the graft copolymers was studied in coal fine suspension through “jar test” procedure, toward its possible application as a novel flocculant for treatment of coal washery effluent. BAR-g-PAM is reported as a novel flocculant that can be used for bulk treatment of coal washery effluents. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41046.