This　work　demonstrates　the　molecular　engineering　of　active　sites　on　a　graphene　scaffold.　It　was　found　that　the　N-doped　graphene　nanosheets　prepared　by　a　high-temperature　nitridation　procedure　represent　a　novel　chemical　function　of　efficiently　catalyzing　aerobic　alcohol　oxidation.　Among　three　types　of　nitrogen　species　doped　into　the　graphene　lattice　-　pyridinic　N,　pyrrolic　N,　and　graphitic　N　-　the　graphitic　sp2　N　species　were　established　to　be　catalytically　active　centers　for　the　aerobic　oxidation　reaction　based　on　good　linear　correlation　with　the　activity　results.　Kinetic　analysis　showed　that　the　N-doped　graphene-catalyzed　aerobic　alcohol　oxidation　proceeds　via　a　Langmuir-Hinshelwood　pathway　and　has　moderate　activation　energy　(56.1　±　3.5　kJ·mol-1　for　the　benzyl　alcohol　oxidation)　close　to　that　(51.4　kJ·mol-1)　proceeding　on　the　catalyst　Ru/Al　2O3　reported　in　literature.　An　adduct　mechanism　was　proposed　to　be　different　remarkably　from　that　occurring　on　the　noble　metal　catalyst.　The　possible　formation　of　a　sp2　N-O2　adduct　transition　state,　which　can　oxidize　alcohols　directly　to　aldehydes　without　any　byproduct,　including　H2O2　and　carboxylic　acids,　may　be　a　key　element　step.　Our　results　advance　graphene　chemistry　and　open　a　window　to　study　the　graphitic　sp2　nitrogen　catalysis.　©　2012　American　Chemical　Society.