Boron　carbon　nitride　(BCN)　is　a　promising　earth-abundant　photocatalyst　for　solar　energy　conversion.　However,　the　photocatalytic　activities　of　BCN　materials　remain　moderate　because　of　the　fast　electron-hole　recombination.　Herein,　an　ordered　BCN　structure　is　fabricated　by　a　facile　one-step　thermal　treatment　strategy.　The　ordered　structure　of　BCN　is　directly　evident　from　powder　X-ray　diffraction　and　high-resolution　transmission　electron　microscopy.　Importantly,　it　is　found　that　the　long-period　ordered　structure　can　intrinsically　accelerate　the　separation　and　transfer　kinetics　of　photogenerated　charge　carriers.　Benefiting　from　these　advantages,　the　ordered　BCN　structure　exhibits　remarkable　performance　for　photoinduced　selective　oxidation　of　benzyl　alcohol　compared　with　the　pristine　BCN　counterpart.　This　work　highlights　the　important　role　of　the　crystal　structure　of　light-harvesting　materials　in　affecting　electron-hole　separation　and　at　the　same　time　points　to　the　ample　potential　for　improving　the　photocatalytic　performance.