The syntheses of Keggin and Dawson-structural phospho-tungsto heteropoly compounds and their Peroxo-derivatives(PCWP), and the catalytic performance over this series of catalysts for the selective oxidation of hexanol to hexylaldehyde are reported. By means of IR, NMR and UV-DRS techniques the catalysts were characterized and a comparison of the structural properties of these catalysts before and after the reaction was made. The correlation between the catalytic performance and the structure of this series of catalysts was discussed as well.