Oligomeric chromium(III)-intercalated titanoniobate has been prepared by the intercalation of propylamine into KTiNbO ₅ followed by substitution of propylammonium for tetramethylammonium and finally refluxing with an aqueous solution of Cr(O ₂ CMe) ₃ . The first chromia-pillared layered titanoniobate was then obtained by calcination of oligomeric chromium(III)-intercalated titanoniobate at 400 °C in a flow of N ₂ . Characterization of chromia-pillared titanoniobate revealed that the material has the porous layered structure with a Brunauer–Emmett–Teller surface area of 122.4 m ² g ^-1 and an interlayer distance of 13.4 Å as well as a narrow pore-size distribution in the range 30–46 Å. The layered structure can be retained up to 500 °C. However, calcination of the oligomeric chromium(III)-intercalated titanoniobate in air at the same temperature led to a product with a low surface area and a small interlayer space. X-Ray photoelectron studies indicate the existence of different states of chromia in the products obtained in the different atmospheres. The IR spectra of the pyridine-adsorbed material and the ammonia temperature-programmed desorption profile demonstrate the presence of a large amount of acid sites with medium strength on the surface of the new chromia-pillared material. Isopropyl alcohol decomposition confirms the existence of only acid sites in the sample.