In　this　study,　the　effect　of　Ce　doping　on　field　emission　properties　of　single　crystal　La0.75Ce0.25B6　field　emission　arrays　(FEAs)　was　studied　by　utilizing　a　combination　of　experimental　and　density　functional　theory　(DFT).　The　spark　plasma　sintering　(SPS)　technology　combined　with　optical　zone　melting　method　were　used　to　prepare　Ce　doped　single　crystal　La0.75Ce0.25B6　with　good　quality,　and　then　uses　femtosecond　laser　direct　writing　technology　to　prepare　a　FEAs　on　its　crystal　surface.　The　single　crystal　quality,　field　emission　performance　FEAs　of　La0.75Ce0.25B6　single　crystal　were　tested.　The　curvature　radius　of　the　prepared　FEAs　with　uniform　morphology　and　surface　nanostructure　is　about　0.5　mu　m.　The　femtosecond　laser　does　not　damage　the　surface　structure　and　phase　of　the　FEAs.　The　field　emission　test　results　of　the　FEAs　indicate　that　its　starting　electric　field　is　1.9　V/mu　m.　The　emission　current　density　with　good　emission　stability　could　reach　1.0　mA　under　the　electric　field　of　6.8　V/　mu　m.　DFT　calculated　results　show　that　Ce　doping　enhances　the　field　emission　performance　of　single　crystal　La0.75Ce0.25B6　FEAs　with　a　lower　work　function　by　optimizing　the　energy　band　structure　(Fermi　level　position　and　electron　effective　mass)　and　4f-5d　electron　orbital　distribution.