The paper concentrates on the study of Mo-V-Te-Nb oxide mixtures by electron microscopy combined with catalytic investigation of these materials in the partial oxidation of propane. Surface texturing of catalyst particles composed of two phases referred to in the literature as M1 and M2 is revealed by high-resolution transmission electron microscopy of high performing catalysts. The chemical composition of the catalyst surface is modified by treatment in water to obtain a significant increment in yield of acrylic acid. A chemical realization of the site isolation concept recurring on a supramolecular arrangement of catalyst and reactant rather than on atomic site isolation is suggested. A complex Mo-V-Te-Nb-O (x) precursor phase carries nanoparticles made from a network of oxoclusters active as catalyst for the conversion of propane to acrylic acid. The designed synthesis of the multi-element oxide bulk and of the surface structure with a different composition than the precursor phase improved the performance by a factor of 4.