The Mixed Ionic and Electronic Conducting (MIEC) membrane reactors are of interest because they have the potential to produce high purity oxygen from air at lower costs and provide a continuous oxygen supply to reactions or/and industrial processes. The study of the dual role oxygen flux and catalytic performance of the unmodified and Ni-coated La0.6Sr0.4Co0.2Fe0.8O3-d hollow fibre membranes (LSCF6428 HFM) in the methane oxidation reactions (i.e., partial oxidation of methane and methane combustion) by using air on lumen side and methane on shell side are shown in this chapter. The LSCF6428 HFM participates not only in the oxygen flux but also in the methane conversion to C2. A Ni-coated LSCF6428 HFM under lean O2/CH4 gradient (i.e., 0.5) showed the production of syngas, carbon dioxide and C2 products in agreement with the thermodynamic calculation. At rich O2/CH4 gradient (i.e., 1.0), the formation of carbon dioxide was facilitated. The main catalytic pathway at lean O2/CH4 gradient and H2 reduction treatment was partial oxidation of methane to C2 and syngas.