Understanding　the　mechanisms　by　which　rare-earth　elements　modulate　the　electronic　structure　and　orbital　filling　of　perovskites　is　essential　for　designing　the　highly　active　catalysts.　Herein,　by　doping　the　A-site　of　LaMnO3　with　Gd3+,　the　B-site　active　center　is　triggered,　which　effectively　improving　the　covalency　of　Mn-O　bond　and　increasing　the　oxygen　vacancy　concentration,　also　boosting　the　eg　orbital　filling　electron　number　of　La0.8Gd0.2MnO3　closer　to　1.　Ultimately,　the　mass　activity　and　turnover　frequency　of　La0.8Gd0.2MnO3　are　2.4　and　4.3　times　higher　than　LaMnO3.　DFT　calculations　show　that　Gd　doping　optimises　the　electronic　structure　of　La0.8Gd0.2MnO3,　resulting　in　modulation　of　the　suitable　intermediate　adsorption　energy,　thus　improving　the　catalytic　activity.　Based　on　these　results,　Zinc-air　cells　were　assembled　with　La0.8Gd0.2MnO3　as　the　cathode　catalyst　and　exhibited　high　capacity　and　cycling　stability.　This　work　provides　a　new　perspective　for　rare-earth　optimised　the　intrinsic　properties　of　perovskites　and　enhance　the　bifunctional　electrocatalytic　performance.