The geometrical and electronic structures of VSi3-/0 clusters have been investigated with the DFT, CCSD(T), and CASSCF/CASPT2 methods. The results showed that the suitable functional to identify the ground states of VSi3-/0 clusters is not the B3LYP but the BP86. At the BP86, CCSD(T), and CASPT2 levels, the ground state of the anionic cluster was the (1)A' ((1)A(1)) of tetrahedral eta(3)-(Si-3)V- isomer, while that of the neutral duster was the 1(2)A' and 1(2)A '' (1(2)E) of the same isomer. The 1(2)A' and 1(2)A '' of the tetrahedral eta(3)-(Si-3)V isomer were the results of the Jahn-Teller distortions of the 1(2)E in C-3v symmetry. All three bands in the photoelectron spectrum of the VSi3- cluster were interpreted by one-electron detachments from the (1)A' anionic ground state on the basis of the BP86, CCSD (T), and CASPT2 methods. The calculated adiabatic and vertical detachment energies were in agreement with the experimental values. The broad shape of the first band was explained by Franck-Condon factor simulations for the (1)A' -> 1(2)A' and (1)A' -> 1(2)A '' transitions within the tetrahedral eta(3)-(Si-3)V-/0 isomers.