We demonstrate grafting of nitroxide radicals on the surface of nanodiamonds (NDs). The surface of NDs is functionalized by azide groups. Nitroxide radicals are covalently bonded using Cu(I)-catalyzed azide/alkyne-click chemistry approach. The reaction is confirmed by infrared spectroscopy. The grafting of nitroxides is also verified by studying the rotational correlational time using electron paramagnetic resonance (EPR) spectroscopy. EPR study estimates that a few hundreds (tens) of nitroxide radicals are grafted on the surface of NDs with 100 nm (25 nm) of the average diameter.