The geometrical and electronic structures of the low-lying states of VSi4/0 clusters as computed with the density functional theory and the multiconfigurational CASSCF/CASPT2 method are reported. The results show that the appropriate functionals to investigate the VSi4/0 clusters are the pure GGA BP86 and PBE functionals, while the hybrid B3LYP and PBE0 functionals underestimate the energies of the high-spin states. All features in the photoelectron spectrum of VSi4 cluster are interpreted based on the oneelectron detachments from the (1)A' of trigonal bipyramid VSi4 isomer in which the V atom is distributed in the equatorial corner of the bipyramid. (C) 2017 Elsevier B.V. All rights reserved.