In this work, the unconsolidated carbon-nitridelayer close-wrapped nanodiamond (H-ND) hybrid has been successfully synthesized by a facile two-step approach including the mechanical milling of ND powder and hexamethylenetetramine and the followed pyrolysis of hexamethylenetetramine. The unique microstructure and surface chemistry characteristics of the nanohybrid have been identified by employing diverse characterization techniques including field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), N 2 adsorption desorption (BET), X-ray diffraction (XRD), Raman spectroscopy (Raman), and X-ray photoelectron spectroscopy (XPS) analyses. Benefiting from the intensified synergistic effect between carbon nitride and nanodiamond, the as-synthesized H-ND hybrid carbocatalyst shows remarkably higher catalytic activity for oxidant-and steam-free direct dehydrogenation (DDH) of ethylbenzene than the nanodiamond (ND) and the previously developed mesoporous carbon nitride, which endows it to be a promising candidate for clean and energy-saving synthesis of styrene through DDH of ethylbenzene. Furthermore, this work also opens a new avenue for fabrication of diverse unconsolidated carbon nitride layers close wrapped nanocarbon hybrids with potential applications for diverse transformations owing to the intensified synergistic effect between carbon nitrides and the nanocarbons.