Electrolytic　manganese　is　an　important　metal　material　that　is　widely　employed　in　batteries,　electronics,　steel,　and　other　fields.　However,　there　are　many　issues　regarding　the　production　process　of　electrolytic　manganese,　such　as　low　current　efficiency,　high-content　toxic　SeO2　additives　in　the　electrolyte,　and　difficulty　in　controlling　the　product　morphology.　These　issues　not　only　impact　the　production　efficiency　and　quality　of　electrolytic　manganese　but　also　result　in　severe　environmental　pollution.　To　address　these　issues,　a　MnSO4-(NH4)2SO4　electrolyte　system　was　prepared　based　on　the　electrolytic　manganese　industry　standard.　The　effects　of　polyacrylic　acid,　glycine,　ethylenediaminetetraacetic　acid　(EDTA),　and　gluconic　acid　were　explored　as　auxiliary　additives　under　neutral　electrolysis　conditions　to　lower　the　SeO2　content,　which　is　a　highly　toxic　main　additive.　The　effects　of　the　different　additives　on　the　metal　manganese　morphology,　crystal　structure,　and　cathodic　electrochemical　polarization　behavior　were　examined　by　field-emission　scanning　electron　microscopy,　X-ray　diffraction,　and　constant　current　cathodic　polarization　curve　tests.　The　findings　reveal　that　the　main　orientation　of　the　metal　manganese　crystal　form　deposited　by　the　four　auxiliary　additives　is　the　(330)　crystal　plane,　and　all　of　them　can　promote　the　formation　of　α-Mn,　enhance　the　electrolysis　efficiency,　and　lower　the　energy　consumption.　In　particular,　the　optimized　amount　of　polyacrylic　acid　of　0.08　g·L−1　contributes　to　an　energy　consumption　of　5735.34　kW·h·t−1.　Correspondingly,　the　addition　of　10　g·L−1　glycine　is　the　most　favorable　amount,　leading　to　an　energy　consumption　of　5518.56　kW·h·t−1.　For　EDTA,　the　lowest　energy　consumption　of　5168.26　kW·h·t−1　is　measured　at　an　added　amount　of　0.5　g·L−1.　Note　that　among　the　four　investigated　candidates,　gluconic　acid　is　the　most　favorable　auxiliary　additive,　contributing　to　the　increased　cathode　current　density　and　reduced　cathodic　polarization　as　well　as　denser　metal　manganese　products.　Moreover,　gluconic　acid　addition　can　lower　the　concentration　of　toxic　SeO2　from　0.03-0.06　to　0.015　g·L−1,　significantly　increase　the　cathode　current　density,　reduce　the　cathodic　polarization,　and　result　in　a　more　dense　and　smooth　product　morphology,　with　the　current　efficiency　being　increased　from　approximately　70%　to　89.73%　and　energy　consumption　being　reduced　from　6500　to　4990.58　kW·h·t−1　at　the　same　time.　Gluconic　acid,　as　the　auxiliary　additive,　not　only　contributes　to　the　best　electrolysis　indexes　for　electrolytic　manganese　but　also　facilitates　the　formation　of　metal　manganese　with　the　most　desirable　crystal　structure.　This　work　offers　novel　insights　into　the　environmentally　friendly　production　and　cheap　electrodeposition　of　metal　manganese　for　the　electrolytic　manganese　industry.　©　2024　Science　Press.　All　rights　reserved.