Layered LnBa(Co,Me)2O5+δ (Ln = Nd, Sm, Ho and Y; Me = Fe, Ni, Cu) with double perovskite structure were synthesized by the solid-state reaction and glycerin-nitrate technique and characterized by X-ray diffraction, thermogravimetric analysis, iodometric titration and dilatometry. Homogeneity ranges for the solid solutions were determined. The oxygen content in LnBa(Co,Me)2O5+δ decreases with decreasing rare-earth cation size. Partial substitution of cobalt by iron increases oxygen content while introduction of copper decrease it. The average thermal expansion coefficients were calculated. Chemical compatibility of studied perovskites with Ce0.8Sm0.2O2 and Zr0.85Y0.15O2 solid electrolytes has been studied.