Understanding　the　intrinsic　relationship　between　photoluminescence　(PL)　properties　and　fine　crystal　structure　is　essential　for　developing　excellent　cerium　doped　Y3Al5O12　(YAG:Ce)　nanophosphors.　Herein,　we　studied　the　crystal　structure　evolution　of　YAG:　Ce　nanophosphors　with　calcination　temperature　via　multiple　characterization　techniques,　and　focused　on　clarifying　the　local　structure　of　Ce3+　activator　by　advanced　quantitative　Al-27　magic　angle　spinning　nuclear　magnetic　resonance　(Al-27　MAS　NMR)　spectroscopy.　The　results　showed　that　the　crystallinity　of　the　YAG:Ce　nanophosphors　was　improved　and　the　lattice　constant　monotonously　decreased　with　rising　calcination　temperature.　Especially,　as　the　calcination　temperature　increased　from　830　to　1030　degrees　C,　more　Ce3+　ions　entered　the　first　sphere　of　AlO6　groups　and　the　symmetry　of　AlO4　species　gradually　increased　in　YAG:　Ce　nanophosphors,　which　caused　the　decrease　of　geometrical　distortion　surrounding　Ce3+　activators.　Due　to　the　variations　of　fine　structure,　the　PL　intensity　obviously　increased　with　calcination　temperature　while　its　position　remained　constant.　When　the　calcination　temperature　further　increased　to　1080　degrees　C,　CeO2　impurity　formed　in　the　nanophosphor,　resulting　in　the　increase　of　the　quenching　centers.　(C)　2017　Elsevier　B.V.　All　rights　reserved.