This work examined the behavior of a novel zeolite augmented on the electrocoagulation process (ZAEP) using an aluminum electrode in the removal of high-strength concentration ammonia (3471 mg/L) from landfill leachate which was saline (15.36 ppt) in nature. For this, a response surfaces methodology (RSM) through central composite designs (CCD) was used to optimize the capability of the treatment process. Design-Expert software (version 11.0.3) was used to evaluate the influences of significant variables such as zeolite dosage (100–120 g), current density (540–660 A/m²), electrolysis duration (55–65 min), and initial pH (8–10) as well as the percentage removal of ammonia. It is noted that the maximum reduction of ammonia was up to 71%, which estimated the optimum working conditions for the treatment process as follows: zeolite dosage of 105 g/L, the current density of 600 A/m², electrolysis duration of 60 min, and pH 8.20. Furthermore, the regression model indicated a strong relationship between the predicted values and the actual experimental results with a high R² of 0.9871. These results provide evidence of the ability of the ZAEP treatment as a viable alternative in removing high-strength landfill leachate of adequate salinity without the use of any supporting electrolyte.