Developing　advanced　cathode　materials　plays　a　positive　role　in　lowering　the　charge/discharge　overpotentials　and　improving　the　cycling　performance　of　lithium–oxygen　batteries　(LOBs).　Here　we　report　a　direct　synthesis　strategy　to　prepare　high-dimensional　branched　PdCoPx　series　nanostructures,　in　which　the　Pd　atoms　are　well　dispersed　within　cobalt　phosphide,　leading　to　rich　Pd─Co─P　interfaces　and　evoking　a　prominent　ligand　effect　between　the　elements.　The　Pd1Co2Px　exhibits　an　excellent　and　stable　activity　for　oxygen　reduction　reaction　(ORR)　in　alkaline　media,　with　a　mass　activity　of　1.46 A　mgPd−1,　far　exceeding　that　of　commercial　Pd/C　(0.12 A　mgPd−1)　and　Pt/C　(0.17 A　mgPt−1).　Using　Pd1Co2Px　as　the　cathode,　the　resulting　LOB　shows　an　ultralow　discharge/charge　overpotential　of　0.40 V　and　could　run　stably　for　over　240　cycles,　which　is　a　significant　improvement　compared　with　the　counterparts　using　CoPx　and　Pd/C　cathodes.　Experimental　and　density　functional　theory　(DFT)　calculation　results　indicate　that　the　dispersed　Pd　atoms　could　significantly　enhance　the　ORR　kinetics,　and　the　Pd─Co─P　interfaces　could　direct　the　two-dimensional　growth　of　Li2O2,　thereby　facilitating　the　formation　of　more　easily　decomposable　film-like　Li2O2　products.　This　feature　successfully　elevates　both　the　charge　and　discharge　performances,　as　well　as　the　stability　of　the　LOB.　©　2025　Wiley-VCH　GmbH.