The hydrolysis behaviors of polyferric sulfate (PFS) and ferric sulfate (FS) under conditions similar to raw wastewater were investigated and the coagulation of biologically pretreated molasses wastewater using PFS and FS was evaluated by studying coagulation efficiency, zeta potential and microscopic surface morphology of flocs. Experimental results show that the hydrolysis behavior of PFS is different from that of FS on the basis of ferron assay. In the case of FS, fast-reacting Fe(III) polymers were the dominant polynuclear species while large fraction of slow-reacting iron polymers is present in PFS. Despite slightly fewer dosages of PFS required as compared to FS, there is no marked difference in the coagulation of molasses effluent between PFS and FS, especially at the optimum dosages. Both coagulants destabilize organic compounds predominantly through charge neutralization-precipitation mechanism. Hydrolysis rate of PFS in synthetic solution is appreciably different from that in raw wastewater. This may due to the effect of sulfate anion introduced as counter-ion as well as depolymerization of larger polymeric Fe(III) species by the organic ligands present in molasses effluent.