The structural evolution and electronic properties of VnC2-/0 and VnC4-/0 (n = 1-6) clusters were investigated using photoelectron spectroscopy and density functional theory calculations. The adiabatic and vertical detachment energies of VnC2- and VnC4 (n = 1-6) clusters were obtained from their photoelectron spectra. The most stable structures were identified by comparing the results of our calculations with the experimental data. We found that the carbon atoms of VnC2-/0 and VnC4-/0 (n = 1-6) clusters were separated gradually with increasing number of vanadium atoms. For VnC2-/0/ (n = 3-6) and VnC4-/0 (n = 4-6) clusters, the carbon atoms are separated by the vanadium atoms. The geometry of V4C4 is a cubic structure and the geometries of V5C4 and V6C4 are formed by one and two vanadium atoms capping the cubic V4C4 structure, respectively.