A series of perovskites of the formula Ca1-xSrxTi1-yMyO3-delta (M = Fe or Co, x = 0-1, y = 0-0.6 for Fe, y = 0-0.5 for Co) were prepared and tested as the catalyst for the oxidative coupling of methane. The catalysts were stable under the reaction conditions. The catalysts of high p-type and oxide ionic conductivity afforded the high selectivity. Some catalysts containing Co on B-sites are thermally unstable and decomposed to metal oxide components at high temperature, giving rise to synthesis gas production.