The bulk defect structure in Cr2-xTixO3 (x = 0.05, 0.20 and 0.30) has been studied by X-ray absorption spectroscopy measurements at the Cr and Ti K-edges. The results show that the Ti is predominantly present in the IV oxidation state and resides on the normal Cr host lattice site. The dopant is charge compensated by Cr3+ vacancies and there is evidence for the formation of defect clusters; however, the detailed structure of these clusters could not be deduced. (c) 2006 Elsevier B.V. All rights reserved.