Dawson type polyoxometallates K 6 P 2 Mo x W 18−x O 62 (x=0, 5, 6) and α1 and α2-K 7 P 2 Mo 5 VW 12 O 62 were prepared and characterized by BET, IR, UV–vis and 31 P NMR spectroscopies and thermal analysis (TG and DTA) and tested in methanol oxidation at 260°C in the presence of molecular oxygen. The Dawson compounds were found to be active in this reaction and the product distribution (formaldehyde, methyl formate, dimethylether, dimethoxymethane) depends on the polyanion composition and on the framework symmetry. α-K 6 P 2 W 18 O 62 exhibits an excellent catalytic performance with ca. 27% of methanol conversion and 98% of dimethylether selectivity. α1-K 7 P 2 Mo 5 VW 12 O 62 and α2-K 7 P 2 Mo 5 VW 12 O 62 show a similar activity (17–19% of conversion) with 49% of methyl formate selectivity and 41% of formaldehyde selectivity respectively. α-K 6 P 2 Mo 6 W 12 O 62 is the most oxidizing catalyst and the most selective toward the methyl formate (ca. 53%).