Dynamics of structural transformation of supported heteropoly compound was investigated by IR-spectroscopy, XRD, TPR, and TPO methods. The 15-30 wt.% H3PMo12O40 and H3PV2Mo10O40, supported on SiO2 catalysts were investigated in process under various conditions by interaction with O2 (air) in the presence of water vapor, H2, alkane in TPR regime, O2 in TPO regime (298-1273K) and H2O (298, 923K). The rank of reversible structural conversion of supported heteropoly compounds was established under influence of temperatureand medium. These new findings of reversible structural cycle explains the stability of the 12th series Mo heteropoly compounds supported on Si-containing carrier at high temperatures (873-1073K) which is close to the actual operation temperatures of the partial oxidation reactions and oxidative dehydrogenation of alkanes.