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The g-shifts Ag( = g-g(s), where g(s) approximate to 2.0023 is the free-ion value) of the isoelectronic 3d(3) series Cr3+. Mn4+ and Fe5+ in SrTiO3 crystals are calculated from the high-order perturbation formula based on the cluster approach for 3d3 ion in cubic octahedral site. The formula includes not only the contribution from the crystal-field (CF) mechanism, but also that from the charge-transfer (CT) mechanism (which is omitted in the CF theory). From the calculations, it is found that the contribution Delta g(CT) from the CT mechanism in sign is contrary to the corresponding Delta g(CF) from the CF mechanism and the relative importance of CT mechanism (characterized by vertical bar Delta g(CT)/Delta g(CF)vertical bar) increases with the increasing valence state (and hence the atomic number) of 3d(3) ion. The positive g-shift Delta g of SrTiO3:Fe5+ is due mainly to the contribution of CT mechanism. So, for the explanations of g factors of the high valence state 3d" ions (e.g. Mn4+ and Fe5+) in crystals, the contributions from both CF and CT mechanisms should be taken into account. (c) 2005 Elsevier Ltd. All rights reserved.