Coagulation/flocculation process was applied in the polishing treatment of molasses wastewater on a bench-scale. Important operating variables, including coagulant type and dosage, solution pH, rapid mixing conditions as well as the type and dosage of polyeletrolytes were investigated based on the maximum removal efficiencies of chemical oxygen demand (COD) and color, residual turbidity and settling characteristics of flocs. HPSEC was utilized to evaluate the removal of molecular weight fractions of melanoidins-dominated organic compounds. Experimental results indicate that ferric chloride was the most effective among the conventional coagulants, achieving 89% COD and 98% color eliminations; while aluminum sulfate was the least effective, giving COD and color reductions of 66% and 86%, respectively. In addition to metal cations, counter-ions exert significant influence on the coagulation performance since Cl--based metal salts attained better removal efficiency than SO42--based ones at the optimal coagulant dosages. Coagulation of molasses effluent is a highly pH-dependent process, with better removal efficiency achieved at lower pH levels. Rapid mixing intensity, rather than rapid mixing time, has relatively strong influence on the settling characteristics of flocs formed. Lowering mixing intensity resulted in increasing settling rate but the accumulation of floating flocs. When used as coagulant aids, synthetic polyelectrolytes showed little effects on the improvement in organic removal. On the other hand, cationic polyacrylamide was observed to substantially enhance the settleability of flocs as compared to anionic polyacrylamide. The effects of rapid mixing conditions and polymer flocculants on the coagulation performance were discussed. (C) 2009 Elsevier B.V. All rights reserved.