Carbon　defects　coupled　with　heteroatoms　can　asymmetrically　rearrange　the　local　electronic　distribution　and　coordination　environment　of　active　sites,　improving　the　catalytic　selectivity　and　activity　of　a　two-electron　oxygen　reduction　reaction　(2eORR).　In　this　study,　an　asymmetry　defective　carbon　(asy-DC)　structure　using　wolfberry　as　the　carbon　source　is　employed　to　adjust　the　charge　distribution　of　active　sites　with　different　degrees　of　asymmetry　caused　by　N→S　coordination　bonds.　The　asymmetric　region　exhibits　a　considerable　positive　correlation　between　the　asymmetry　degree　and　adsorption　energy　for　OOH*,　presenting　a　volcano　relation　between　the　asymmetry　degree　and　catalytic　activity.　The　optimised　asy-DC　catalyst　exhibits　high　selectivity　and　reliable　activity　after　12　h　of　stability　testing.　This　study　can　provide　a　new　reference　into　the　origin　of　ORR　activity　and　selectivity.　©　2024　Elsevier　B.V.