Abstract A robust monolith catalyst has been fabricated involving the combination of nanodiamonds (NDs) and mesoporous carbon modified by nitrogen and phosphorus (ND@NMC-xP, x = amount of ammonium biphosphate) on a β-SiC foam. The ND@NMC-0.02 P/SiC monolith catalyst with 0.2 at.% of P elements exhibits an excellent catalytic performance for oxidative dehydrogenation of ethylbenzene (EB), delivering 90.2% selectivity to styrene (ST) up to 32.6% conversion. The specific conversion rate of monolith catalyst based on the unit weight of NDs and mesoporous carbons (25.3 mmol gact. phase−1 h−1) is 3-fold higher than that of unsupported NDs. The role of nitrogen is believed to enhance the density of active sites and thus offering a high EB conversion, whereas the addition of phosphorus inhibits deep oxidation of EB to carbon oxides and therefore for a high selectivity to ST. The monolith catalyst not only contributes a high utilization efficiency of NDs but also mitigates the high pressure drop across the catalytic bed, which is potentially suitable for a real industrial process.