The photoluminescence of intentionally vanadium-doped ZnSe crystals displays at low temperatures (T approximately=4 K) the emission of the V³⁺ (d²), V²⁺ (d³) and V⁺ (d⁴) ions with different no-phonon structures at 5440, 4740 and 3640 cm^-1, respectively. The excitation spectra of the V³⁺ and V²⁺ luminescence bands are investigated separately and exhibit structures of the respective spin-allowed as well as spin-forbidden internal transitions, which are largely in accordance with those of ZnS:V. The corresponding energy levels are approximated in a computation following the Tanabe-Sugano scheme. Furthermore, charge transfer processes at the luminescent centres are manifest in excitation, stimulation and transmission spectra. The vanadium ion proves to be an amphoteric impurity. Commencing from V²⁺, the state with neutral effective charge, light-induced transitions of donor and acceptor type are disclosed: V²⁺ to or from V³⁺+e_CB^- and V²⁺ to or from V⁺+e_VB⁺.