Abstract Applying inorganic metal salt-based aluminium sulphate (Al2(SO4)3) or alum in wastewater treatment has gained many concerns regarding the impact on health and environmental implications. Due to the negative consequences, incorporating inorganic and natural flocculants in the coagulation-flocculation process is the alternative way to reduce undesirable effects. In this study, an evaluation performance of Manihot esculenta (ME) starch and alum as a dual flocculant was conducted to remove chemical oxygen demand (COD) in the optimum weight ratio of alum/starch = 0.06. The optimization of coagulation-flocculation by the optimal (custom) design, response surface methodology (RSM) presented that applying a dual flocculant improved the COD removal efficiency by up to 93% compared to a single coagulant (alum) of 85%. Besides the performance of COD removal increased, the dosage of the chemical coagulant was reduced by up to 64% at the optimum condition of 18 mg/L alum dosage, 307 mg/L starch dosage, pH 9, and 27 mins settling time. The analysis of variance (ANOVA) indicated that the quadratic model was significantly developed with a p-value < 0.05. The results were justified by a high coefficient of determination (R2 alum = 0.9641) and (R2 dual flocculants = 0.9335) using single and dual flocculants, respectively. The findings supported ME starch as an alternative approach in minimizing chemical coagulants in wastewater treatment.