Density functional theory and the multiconfigurational CASSCF/CASPT2 method, have been employed to study the low-lying states of VGen-/0 (n > 1-4) clusters. For VGe2-70 and VGen-/0 clusters, the relative energies and geometrical structures of the low-lying states are reported at the CASSCF/CASPT2 level. For the VGe3-/0 and VGe-70 clusters, the computational results show that due to the large contribution of the Hartree-Fock exact exchange, the hybrid B3LYP, B3PW91, and PBE0 functionals overestimate the energies of the high-spin states as compared to the pure GGA BP86 and PBE functionals and the CASPT2 method. On the basis of the pure GGA BP86 and PBE functionals and the CASSCF/CASPT2 results, the ground states of anionic and neutral clusters are defined, the relative energies of the excited states are computed,- and the electron detachment energies of the anionic, clusters are evaluated. The computational results are employed to give new assignments for all features in the photoelectron spectra of VGe3- and VGe4- clusters.