Ce4+ doped Ba3WO6 complex oxides were used as catalysts for methane oxidative coupling (MOC), and characterized by XPS and O2-TPD-MS techniques. The results indicate that the ratio of electrophilic oxygen species O- and O2- to lattice oxygen on the surface is crucial for C2 selectivity. By adjusting the relative amount of cations in Ba-W-Ce complex oxides with perovskite superstructure interstitial oxygen species can be created which benefits C2 selectivity by raising the relative amount of (O- + O2-) on the surface.