Perovskite-type oxides of composition BaTi0.9Rh0.1O3 +/-delta were prepared following a new chemical route that avoids the formation of hydroxyl species and precipitation, and allows the homogeneous distribution of Rh in the final mixed metal oxide. The high dispersion of Rh and the formation of the solid solution between Rh and the BaTiO3 perovskite is confirmed by means of X-ray diffraction (XRD) and extended X-ray absorption fine structure spectroscopy (EXAFS). The presence of Rh stabilized the hexagonal BaTi0.9Rh0.1O3 +/-delta phase, which decomposes into barium orthotitanate (BaTi2O4) and metallic Rh degrees in reducing environment. This phase transition starts already at 700 degrees C and is only partially completed at 900 degrees C suggesting that part of the Rh present in the perovskite lattice might not be easily reduced by hydrogen. These aspects and further open questions are discussed. (C) 2014 Elsevier Ltd. All rights reserved.