Powder BaAl2O4 samples doped with 0 and 1.76 atom % Cr in relation to Al were hydrothermally prepared. Both samples were characterized by X-ray diffraction and synchrotron based X-ray absorption spectroscopy at the Cr K- and the Ba L-3-edge. Diffraction patterns indicated that samples were nanocrystalline with a hexagonal crystal structure, space group P6(3). Chromium doping of barium aluminate caused an increase of the unit-cell volume and diffraction line broadening. The doped sample contained a small amount of an impurity phase, namely, BaCrO4. Analyzed Cr K-edge X-ray absorption near edge structure for the doped sample showed the presence of chromium in 6+ and 3+ oxidation states: Cr6+ was characteristic for chromium in the impurity phase BaCrO4, while Cr3+ participated in the formation of the doped phase BaAl2O4:Cr. Extended Xray absorption fine structure suggested an unusual tetrahedral coordination of Cr3+ ions within the BaAl2O4 host phase. The structure of samples was refined by the Rietveld method, simultaneously with the analysis of diffraction line broadening. Rietveld structure refinement showed that in doping the Cr3+ ions likely substituted for Al3+ ions on All tetrahedral sites of barium aluminate crystal lattice. Crystallite sizes in the samples decreased with chromium doping, from 32 nm for pure BaAl2O4 to 24 rim for Cr-doped BaAl2O4. The dopant Cr3+ cations acted as defects in the barium aluminate structure that increased lattice strain from 0.02% for pure BaAl2O4 to 0.14% for doped BaAl2O4 and disturbed the crystallites to grow.