Using density functional theory (DFT) with valence basis set LANL2TZ to study the relative stabilities and electronic properties of the most stable structures of NbnV(0, ±1) (n = 1−6) clusters. The ground state structures of NbnV (0, ±1) keep the similar geometric structure as the host Nbn clusters. The doping of vanadium atom enhances the chemical activities of Nbn clusters. The Nb3V and Nb6V are more stable than other clusters. The average binding energy of charged systems (NbnV+ and NbnV− clusters) are generally larger than neutral NbnV clusters natural population analysis shows that there are charge transfers from niobium to vanadium atoms in the small Nb1−4V, however, for larger clusters (Nb5V and Nb6V), the charge transfers are from vanadium to niobium atoms. The vertical and adiabatic ionization potentials (VIP and AIP) are estimated and the vertical one is more close to experimental results.