Lithium-rich　layered　oxides　(LLO)　have　drawn　increasing　attention　as　one　of　the　most　promising　cathodes　for　next-generation　high-energy-density　lithium-ion　batteries　(LIBs).　However,　they　are　plagued　by　low　initial　Coulombic　efficiency　(ICE)　and　terrible　cyclic　stability　due　to　their　intrinsic　irreversible　oxygen　release.　Herein,　to　enhance　the　comprehensive　electrochemical　performance　of　LLO,　an　effective　strategy　is　brought　up　to　regulate　the　interfacial　oxygen　coordination　environment　via　lithium　deficiencies,　Na+　ion　doping,　as　well　as　the　induced　Li+/Ni2+　antisite　defects　and　in-situ　epitaxial　grown　spinel　phase.　The　density　functional　theory　calcu-lations　(DFT)　confirm　that　the　existence　of　lithium　deficiencies　and　Na+　ions　doping　can　decrease　the　diffusion　energy　barrier　of　Li+　ions.　Meanwhile,　the　regulated　oxygen　coordination　environment　results　in　an　increase　in　the　oxygen　vacancy　formation　energy,　which　is　beneficial　for　the　improvement　of　the　lattice　oxygen　stability　in　the　deeply　charged　state.　As　a　result,　the　modified　sample　exhibits　high　initial　coulombic　efficiency　of　91.2%　and　good　capacity　retention　of　95.3%　after　400　cycles　at　1C　(1C　=　250　mA　g-1).　This　work　offers　a　new　idea　for　designing　advanced　LLO　cathodes,　which　could　promote　their　practical　applications　in　high-energy-density　LIBs.