The present study treated compost leachate, a high load organic and inorganic wastewater, using a batch electrocoagulation–flotation (ECF) process. ECF is an effective, fast, reliable, feasible, and economic technique for wastewater treatment. The interactive effects of operational factors such as influent chemical oxygen demand (COD), voltage, electrolysis time (ET), and electrodes distance (ED) on the efficiency of COD and total suspended solid (TSS) removal for various electrodes configurations (Al–Al, Al–Fe, Fe–Al, Fe–Fe) were analyzed and correlated. Al–Al was found to be the best configuration based on maximum removal of COD and TSS. Ultimately, analysis of associated results indicated that the best arrangement (Al–Al) possessed the following optimal factors: influent COD = 12,627 mg/L, voltage = 19 V, ET = 75 min, and ED = 3 cm for maximum removal of COD (96%) and TSS (99%). Confirmation tests indicated a 95% confidence interval for good agreement of the experimental results and predicted values from fitted correlations. Analysis of outcomes demonstrated that COD concentration was the most effective variable for COD and TSS removal, and, in addition, an increase in ET and a decrease in ED had positive effects. Total corrosion on the Al and Fe plates was 34.8 and 146.6 g, respectively.