Gadolinium-doped cerium oxide (CGO) and lanthanum strontium manganate (LSM) are electro-ceramics materials with high potential for several electrochemical applications such as solid Oxide Fuel Cell (SOFC), gas separation membranes, and flue gas purification devices. Especially for novel electrochemical flue gas purification devices, multilayer structures with alternating porous layers of CGO and a LSM/CGO mixture are used to achieve specific functional requirements. In a manufacturing process of such ceramic multilayer devices, co-firing is one of the critical steps as many defects such as cracks, de-lamination and shape distortion can result as a consequence of sintering mismatch stresses caused by the strain rate difference between layers. This work seeks to understand the underlying mechanisms that occur during the co-firing of porous CGO-LSM/CGO bi-layer laminates, by evaluating the sintering mismatch stress and distortion development through modeling and experiments.