In an attempt to develop new catalysts for the formation of formaldehyde from methane, the promotion effect of Fe on SiO2 and that of Sn on WO3 have been studied. The formation of formaldehyde on silica can be appreciably enhanced by the impregnation of Fe, as far as iron loadings are kept below 0.1 atom.% (Fe/Si x 100). In the case of Sn-W-Ox catalysts, both the addition of Sn to WO3 and that of W on SnO2 were effective to the selective formaldehyde formation. Absorption spectra (UV-Vis) and ESR measurements revealed that tetrahedrally coordinated Fe3+ in the silica network plays an important role in the formation of formaldehyde. A thin surface layer consisting of W and Sn oxides can account for the selective formaldehyde formation on the Sn-W-Ox catalysts.