The pigments (melanoidins) in molasses wastewater are refractory to conventional biological treatment. Ferric chloride was used as coagulant to remove color and chemical oxygen demand (COD) from molasses effluent. Using jar test procedure, main operating conditions such as pH and coagulant dosage were investigated. Under the optimum conditions, up to 86% and 96% of COD and color removal efficiencies were achieved. Residual turbidity in supernatant was less than 5 NTU and Fe³⁺ concentration was negligible because of effective destabilization and subsequent sedimentation. The results of high performance size exclusion chromatography (HPSEC) show that low molecular weight (MW) fraction of melanoidins is more reactive than high MW fraction and increase in the concentration of the lowest MW organic group is related to the capacity of charge neutralization. Aggregate size measurement reveals the size effect on the settleability of flocs formed, with larger flocs settling more rapidly. Charge neutralization and co-precipitation are proposed as predominant coagulation mechanism under the optimum conditions.