Dehydrogenation coupling of methane (DCM), which can be effectively used to produce low carbon alkenes, has the advantages of rich raw materials, simple reaction device, low energy consumption, etc. Herein, we report a series of Co doped perovskite porous-dense BaCe_0.9Y_0.1Co_xO_3-δ (BCYCx) membrane for DCM. After treatment in a reduced atmosphere, a large number of Co nanoparticles will exsolute on the surface of BCY. The metal-oxide interface is helpful to activate the C–H bonds, inhibit the carbon deposition, and so on. The XRD, SEM and XPS prove that Co nanoparticles homogeneously distributed on the BCYCx porous layers, which will create a large quantity of catalytic active sites. At 1100 ℃, the highest concentration of C₂ product was 5.66% (5.25% ethane + 0.41% ethylene) in output gas when methane conversion reaches a maximum value of 24.8%, and the C₂ selectivity gets to 45.6%. We further demonstrate the catalytic performance of high-temperature DCM without obvious decrease after running for 30 hours.