This paper describes a new method for the recovery of high-concentration ammonia from water in the form of ammonium chloride, ammonium hydroxide and ammonium carbonate. The method was applied to the Solvay process, in which sodium bicarbonate is produced through the reaction of ammoniated brine and CO2 gas. The Solvay effluent contains ammonia in the form of soluble ammonium chloride. The proposed method is based on the recovery of ammonia using a high-alkalinity reactant, calcium oxide (CaO), in a closed electrocoagulation cell operating at a specific current density. The recovered ammonia is collected as a gas within a closed cell containing deionized (DI) water at room temperature. Afterwards, the collected solution (DI water–NH3 gas) is concentrated through a separate process, and is then reused in the Solvay process and other applications. The electrocoagulation process is applied to the treatment cell using aluminum electrodes and a current density of 5–15 mA/cm2. After 7 h of treatment using the electrocoagulation cell, a high reduction of the ammonia concentration—99%—was realized after ~9 h of the electrochemical treatment. The initial ammonia concentration in a Solvay effluent of 13,700 mg/L N was decreased to 190 mg/L N. Furthermore, an ammonia recovery of 77.1% in the form of ammonium hydroxide was achieved. Generally, this process, which starts at room temperature, can result in an energy reduction of 80%—from 7.8 to 2.3 kWh/kg NH3—compared to conventional processes, which entail heating the Solvay effluents to 160 °C. The proposed system and method were found to be suitable for the recovery of ammonia from ammoniated water, and can be utilized for the treatment of landfill leachate, and municipal and industrial wastewater.