Hybrid materials consisting of few-layer sp(2) carbon supported on Al2O3 can potentially display comparable performance with nanodiamonds for the oxidative dehydrogenation of ethylbenzene. The hybrid structure could be easily prepared by fast coking method using ethanol as a precursor and gamma-Al2O3 with high specific surface areas as a template. In this case, gamma-Al2O3 plays the role of 3D support for depositing few-layer graphene-like structure. The hybrid structure exhibiting similar structure with nanodiamonds calcined at high temperature is further used as a metal-free catalyst for the oxidative dehydrogenation of ethylbenzene to styrene. The yield rate of styrene normalized by the specific area on Al2O3@C is 0.044 mmol m(-2) h(-1) (TOF = 4.13 h(-1)) which is two times of that on nanodiamonds (0.020 mmol m(-2) h(-1), TOF = 3.27 h(-1)). Considering the low cost process and good catalytic performance, the hybrid nanostructure may be a promising candidate to be applied in the oxidative dehydrogenation of ethylbenzene. (C) 2017 Elsevier B.V. All rights reserved.