MoO3/V2O5/TiO2 (anatase) catalyst with 5 and 20 wt.% loadings of MoO3 and V2O5 has been studied, using high resolution electron microscopy. Main structural peculiarity of this system was found to be the presence of nanometer size layers of a complex Mo-V-O phase on the surface of the titania support. The observed structure seems to be a metastable and may exist only on the surface of TiO2 particles.