In the present work we report on the combined experimental and theoretical studies of the optical properties of α-ZnAl2S4 spinel doped with V3+ ions. The studied samples (both with and without vanadium) were grown by the chemical vapor transport method. The undoped ZnAl2S4 crystals were colorless, whereas the V-doped samples were brown. The optical absorption spectra for both un-doped and V-doped α-ZnAl2S4 were recorded at room temperature using a Perkin Elmer Lambda 900 spectrometer in the wavelength range 300–1700 nm. Theoretical analysis of the obtained spectra was performed using both the exchange charge model of crystal field (CF) [1] and ab initio-based CASTEP module [2] of Materials Studio. An essential feature of the performed analysis is that it allowed for a reliable estimation of the position of the lowest V3+ energy level (1.36 eV above the valence band’s top, [3]) with a subsequent positioning of all excited states of V3+ ions, which were derived from the CF calculations. The obtained results are summarized in Figure 1, which shows the experimental and calculated absorption spectra of ZnAl2S4:V3+ along with the band structure of the host with superimposed energy levels of impurity. Fig. 1.Fig. 1. Experimental and calculated absorption spectra of ZnAl2S4:V3+ (left, the vanadium energy levels are shown by the vertical lines). Calculated band structure of ZnAl2S4:V3+ (right, the vanadium energy levels in the band gap and conduction band are shown by the horizontal lines). [1] B.Z. Malkin, in: A.A.Kaplyanskii, B.M. Macfarlane (Eds.), Spectroscopy of solids containing rare-earth ions, North-Holland, Amsterdam, 1987, p. 33. [2] M.D. Segall, P.J.D. Lindan, M.J. Probert, C.J. Pickard, P.J. Hasnip, S.J. Clark, M.C. Payne, J. Phys.: Condens. Matter. 14 (2002) 2717. [3] M.G. Brik, M. Nazarov, Ahmad Fauzi M.N., L. Kulyuk, S. Anghel, K. Sushkevich, G. Boulon, J. Lumin. (in press, http://dx.doi.org/10.1016/j.jlumin.2012.04.044 )