A2B2O7 compounds with tailored compositions exhibit catalytic properties in a variety of high-temperature reactions, such as oxidative coupling of methane (OCM). La2Ce2O7 performs well in OCM due to selective mobile oxygen species, and suitable alkaline sites. Doping with Ca2+ increases the alkalinity, which can considerably increase selectivity for C2 products in OCM. We have explored the combustion synthesis to obtain homogeneous Ca2+-doped La2Ce2O7 materials to use as a catalytic layer in SOFC reactors for methane direct conversion to C2. The addition of Ca2+ in the A site of La2Ce2O7 resulted in the disordered fluorite-type crystalline structure. The formation of superficial oxygen vacancies related to the active oxygen species, which may benefit the OCM reaction, was detected. Electrochemical characterization showed no significant dependence of the conductivity with Ca2+-doping.Funda????o de Amparo ?? Pesquisa do Estado de S??o Paulo (FAPESP)FAPESP: 17/11937-4