In this paper, we report a simple synthesis of four new nickel boride-based nanocomposites, namely Ni2B@ZrCl4, Ni2B@Cu2O, Ni2B@CuCl2 and Ni2B@FeCl3, from commercially available and cheap starting materials. All of the new Ni2B-based nanocomposites were well characterized by Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. Further, the catalytic applications of these new nanocomposites were successfully evaluated in the wet-solvent-free reduction of aromatic nitro compounds to arylamines with sodium borohydride (NaBH4) at room temperature by a mechanochemical grinding technique. All the introduced catalytic systems provide excellent yields of arylamines in very short reaction times for a wide range of substrates. Also, recoverability and reusability of the new nanocomposites were investigated.