The synthesis and characterization of a novel vanadoaluminosilicate, [V,Al]-MCM-22, with MWW structure has been performed. As-synthesized, calcined, and H+ and Na+ ion-exchanged materials were characterized by various techniques, including X-ray diffraction (XRD), scanning electronic microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The presence of redox sites (V4+/V5+ couples) after oxidation in O-2 at 580 degrees C and reduction in H-2 at 500 degrees C was monitored by diffuse reflectance (DR) UV-vis spectroscopy and by F-FIR of CO adsorption at 100 K. Preliminary catalytic tests on the oxidative dehydrogenation (ODH) of propane provided promising results. (c) 2006 Published by Elsevier Inc.