A facile and scalable approach to efficiently tune microstructure and surface chemical properties of N-doped carbocatalysts through the controlled glucose hydrothermal treatment with diverse parameters and subsequent pyrolysis of pretreated carbonaceous materials with melamine (GHT-PCM) was presented. Various characterization techniques including high resolution transmission electron microscopy (HRTEM), N-2 adsorption desorption (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy (Raman), and fourier transform infrared spectroscopy (FTIR) were employed to investigate the effect of prior GHT on the microstructure and surface chemical properties of N-doped carbocatalysts, as well as to reveal the relationship between catalyst nature and catalytic performance in oxidant- and steam-free direct dehydrogenation (DDH) of ethylbenzene for styrene production. It was found that the GHT process and its conditions significantly affect microstructure and surface chemical properties of the N-doped carbocatalysts, which subsequently influences their catalytic performance in DDH reaction dramatically. Interestingly, the prior GHT can remove the carbon nitride layer formed on parent nanocarbon in the process of melamine pyrolysis, produce structural defects, and tune surface element component, through the detonation of polysaccharide coating on nanocarbon. The as-prepared N-doped CNT (M-Glu-CNT) by the established GHT-PCM approach demonstrates higher catalytic performance (4.6 mmol g(-1)h(-1) styrene rate with 98% selectivity) to the common N-doped CNT (M-CNT, 3.4 mmol g(-1) h(-1) styrene rate with 98.2% selectivity) as well as to pristine CNT (2.8 mmol g(-1) h(-1) styrene rate with 96.8% selectivity), mainly ascribed to increased structural defects, enriched surface ketonic CO groups, and improved basic properties from N-doping on the M-Glu-CNT, those strongly depend on GHT conditions. The excellent catalytic performance of the developed M-Glu-CNT catalyst endows it with great potential for future clean production of styrene via oxidant- and steam-free conditions. Moreover, the directed GHT-PCM strategy can be extended to the other N-doped carbonaceous materials with enhanced catalytic performance in diverse reactions by tuning their microstructure and surface chemistry. (c) 2015 American Institute of Chemical Engineers AIChE J, 61: 2543-2561, 2015