Manipulating　the　local　electronic　structure　is　employed　to　address　the　capacity/voltage　decay　and　poor　rate　capability　of　Li-rich　layered　cathodes　(LLOs)　via　the　dual-doping　of　Na+　and　F-　ions,　as　well　as　the　regulation　of　Li+/Ni2+　intermixing　and　the　content　of　＂Li-O-Li＂　configuration.　The　designed　cathode　exhibits　a　high　initial　Coulombic　efficiency　of　about　90%,　large　specific　capacity　of　296　mAh　g(-1)　and　energy　density　of　1047　Wh　kg(-1)　at　0.2　C,　and　a　superior　rate　capability　of　222　mAh　g(-1)　at　5　C　with　a　good　capacity　retention　of　85.7%　even　after　500　cycles.　And　the　operating　voltage　is　increased　without　compromising　the　high-capacity　advantage.　Such　improved　electrochemical　performances　primarily　result　from　the　band　shift　of　the　TM　3d-O　2p　and　non-bonding　O-2p　to　lower　energy,　which　would　decrease　Li+,　diffusion　activation　energy　and　increase　oxygen　vacancy　forming　energy,　finally　improving　the　Li+,　diffusion　kinetics　and　stabilizing　lattice　oxygen.　Moreover,　the　increased　＂Li-O-Li＂　configuration　in　the　Li2MnO3　phase　via　increasing　the　Mn　concentration　can　increase　the　reversible　capacity　to　offset　the　negative　effect　of　inactive　doping　and　Li+/Ni2+　intermixing.　This　strategy　of　modulating　the　local　electronic　structure　of　LLOs　provides　great　potential　to　design　high-energy-density　Li-ion　batteries.