Mo-doped　LiFePO4　was　prepared　using　(NH4)(6)Mo7O24　center　dot　4H(2)O　as　doping　starting　material　by　solid　state　method　under　N-2　atmosphere.　The　Mo-doped　LiFePO4　samples　were　characterized　by　X-ray　diffraction,　scanning　electron　microscope.　X-ray　photoelectron　spectrum,　extended　X-ray　absorption　fine　structure,　positron　annihilation　technique,　and　electrochemical　performance　testing　at　different　discharge　rates.　The　results　showed　that　Mo-doped　LiFePO4　preserved　pure　olivine　structure.　Mo6+　occupied　Fe　site　and　Li　site　simultaneously　and　the　electronic　conductivity　of　LiFePO4　increased.　The　Mo-doped　LiFePO4　had　a　reversible　capacity　141　mAh　center　dot　g(-1)　at　1C　discharge　rate,　and　showed　good　electrochemical　properties.