In order to treat the complex wastewater containing organic compound and solids, pre-treatment system associated with molecular separation process were investigated. The reductions of COD and turbidity were obtained after coagulation processes using Alum (Aluminium sulfate, $Al_2(SO_4)_2{cdot}18H_{2}O$) and PACl (poly aluminium chloride as 17% $Al_{2}O_{3}$). The results of study were as follows: using variable dosage of Alum, COD removal was highest at 4,000 mg/l, and the reduction of COD and turbidity was 42% and 92%, respectively. The optimum coagulation would be effective at pH 7.3 than pH 9.0 by the addition of alum at a concentration of 6,000 mg/l and PACl was add at 4.25% in raw complex wastewater with 2,000 mg/l alum at pH 7.3, the reduction of COD was reduced by 32%. But coagulation aid experiments indicated that PACl would be more effective in sludge separation ability than COD removal efficiency.