The　relationship　between　the　interactions　of　valence,　electronic　structure　and　orbitals　generated　by　rare-earth　doped　perovskites　and　the　electrocatalytic　mechanism　is　important　research　work.　Herein,　the　experimental　and　theoretical　studies　prepared　through　La1-xSmxMnO3　show　that　the　doping　of　Sm　triggers　the　B-site　active　center,　which　will　promote　the　ORR　and　OER　kinetics　at　the　catalyst　interface,　and　ultimately　give　La0.7Sm0.3MnO3　(LSM0.3)　which　has　the　most　positive　half-wave　potential　of　0.70　V　versus　RHE　and　the　smallest　overpotential　of　0.48　V.　Meanwhile,　the　specific　electron　configuration　of　Sm　reduces　the　grain　boundary　energy　and　suppresses　Oswald　maturation,　which　causes　the　smallest　reduction　for　ORR　current　density　during　long-term　operation.　Finally,　zinc-air　cell　assembled　with　LSM0.3　as　a　cathode　catalyst　can　be　cycled　stably　for　330　h　at　1　mA　cm(-2).　This　work　provides　new　insight　into　the　improved　electrocatalytic　performance　of　oxygen　by　rare-earth　doped　perovskites.