Mn/Na 2 WO 4 /SiO 2 catalyst for the oxidative coupling of methane has been investigated by using theL-edge and theK-edge XAFS and XPS. The surface of the fresh catalyst is found to be dominated by oxygen-enriched amorphous phases consisting of discretely distributed tetrahedral WO 4 and octahedral MnO 6 groups. The average bond lengths, which is 1.77 Å for W–O and 2.00 Å for Mn–O, are fully identical to those in pure Na 2 WO 4 and Mn 2 O 3 . However, on the used catalyst after a 450 h run, almost no tungsten species is detectable. Instead, tetrahedral manganese sites are observed. The surface of the used catalyst is dominated by highly dispersed MnO 4 groups consisting of tetrahedral and coordinatively unsaturated octahedral sites. The average Mn–O bond length increases to 2.09 Å while the Mn 2p 3/2 binding energy increases from 641.4 eV (Mn 3+ ) to 641.7 eV (Mn 2+ ). These results suggest that the combination of tetrahedral and octahedral metallic cores with different oxidation states from each other is responsible for the catalysis in the oxidative coupling of methane, and that the high activity of the manganese-tungsten catalyst is due to the surface oxygen species, which are pre-activated from lattice oxygens to “the nearest oxygens” by the surface in an amorphous state.