Metallic vanadium nanoparticles stabilized with 4-octylphenyldiazenido groups (particle size: 1.7 +/- 0.2 nm) were synthesized via the reduction of VCl4 with superhydride (LiBHEt3) in the presence of 4-octylphenyldiazonium salt in an Ar-filled glovebox. The resulting particles were characterized using TEM, elemental analysis, and XPS measurements. The unusual reaction on the surface resulted in the passivation of V-N=N-Ar covalent bonds.