The unique performances of supported rhenium oxide catalysts for the selective oxidation of methanol to methylal (dimethoxymethane) [3CH(3)OH + 1/2O(2) --> CH2(OCH3)(2) + 2H(2)O] were examined in a fixed-bed flow reactor and in a pulse reactor. Rhenium. oxides supported on alpha-Fe2O3, gamma-Fe2O3, and V2O5 among many oxide supports showed high activities (15-49% conversion) and selectivities (90-94% selectivity) for catalytic methylal synthesis at 513 K. These Re catalysts are the first to show good performances for one-stage methylal synthesis from methanol. The catalysts were characterized by XRD, XPS, TPR, TPD, and FTIR spectroscopy to provide insight into the active Re species relevant to the selective oxidation of methanol to methylal. Rhenium oxides on alpha-Fe2O3 were dispersed as tetrahedral ReO4 species up to one monolayer at 0.7 wt % Re loading. It was suggested that active Re-Fe-O mixed-oxide clusters were formed above 1 wt % Re. ReO2 crystallites were also observed for the Re/alpha-Fe2O3 samples with Re loadings above 6 wt %. On gamma-Fe2O3, which has a higher surface area, no ReO2 species were observed. It is suggested that the redox capability of rhenium oxides, Re6-7+ reversible arrow Re4+, is responsible for the catalytic performance, although appropriate Lewis acidity of the rhenium oxides is also necessary for the acetalization of formaldehyde with methanol to methylal. The oxide supports prevent rhenium oxides from being sublimated and reduced to ReO2 particles.