The Electrolytic Manganese Residue (EMR) is a by-product of the electrolytic manganese metal (EMM) industry, containing high concentrations of potential pollutants such as NH4+-N and soluble Mn2+. These components pose a serious threat to the ecological environment. To explore accurate, efficient, and harmless treatment methods for EMR, this study proposes a low-temperature thermochemical approach. The orthogonal experiment design investigates the effects of reaction temperature, reaction time, CaO, Na2CO3, Na3PO4, and water consumption on manganese solidified and ammonia removal from EMR. The results indicate that optimal conditions are a reaction temperature of 60℃ and a reaction time of 10 minutes. CaO precipitates Mn2+ as Mn(OH)2, achieving effective manganese solidified and ammonia removal. The addition of Na2CO3 causes Mn2+ to form MnCO3 precipitate, while Na3PO4 makes Mn2+ form Mn3(PO4)2·3H2O. Increased water consumption enhances the interaction adequacy between ions. Under optimal conditions (CaO 10%, Na2CO3 1%, Na3PO4 0.5%, and 80% water consumption), the removal rate of ammonium ions reaches 98.5%, and the solidification rate of soluble Mn2+ is 99.9%. The order of influence on ammonium ion removal is CaO > water consumption > Na3PO4 > Na2CO3. This study provides a novel approach for the efficient and environmentally friendly harmless treatment of EMR.