Nanodiamonds (NDs) are recognized as a class of robust metal-free catalysts for the steam-free, direct dehydrogenation (DDH) of ethylbenzene (EB) to styrene (ST). In spite of that, some main drawbacks, such as their powdery form along with their tendency to form aggregates, limit their full exploitation at the industrial level. In this work, we describe the preparation of macroscopically shaped monoliths consisting of silicon carbide-based foams coated with a nitrogen-rich mesoporous carbon matrix (NMC) as a non-innocent glue for highly dispersed ND fillers. The NMC phase is prepared from cheap and nontoxic food-grade components and it prevents the undesired NDs agglomeration thus maximizing the reagents exposure throughout the catalytic DDH tests. Moreover, the NMC phase represents a key source of surface basicity capable of inhibiting the occurrence of EB cracking side reactions during the catalytic runs. As a result, the ND@NMC/SiC composite shows excellent dehydrogenation performance already at low ND loading if compared with the powdery NDs and/or the SiC-supported NDs of the state-of-the-art. Noteworthy, the ND@NMC/SiC composite presents its best catalytic performance under DDH conditions close to those used in industrial plants (reaction temperture up to 600 degrees C and EB concentrations up to 10 vol.%) with high ST rates (lambda(catal). of 9.9 mmol(ST gcat)(-1) h(-1)), ST selectivity over 96% and long term stability on stream. (C) 2016 Elsevier B.V. All rights reserved.