The effect of La-deficiency and Ce/Sr-substitution in the benchmark LaCo0.8Fe0.2O3 has been investigated for the decomposition of N2O between 500 and 900 °C. Real inlet gas composition and space velocity reveal that La-deficiency and Ce/Sr-substitution can improve the thermal stability of catalyst, while La1-xSrxCo0.8Fe0.2O3 with x≥0.1 was highlighted as a promising formula due to the strongest resistance to deactivation and suppressed undesired NOx decomposition at high space velocity. This phenomenon is mainly ascribed to the incorporation of Sr2+ into the perovskite lattice during the reaction consequently stabilizing the Co3+ species and creating the oxygen vacancies in La1-xSrxCoO3-δ. On the contrary, the loss of activity on Ce-substituted LaCo0.8Fe0.2O3 has been preferentially related to the cobalt exsolution to extra framework of perovskite making the catalytic cycle with Co3+ unfavorable. All these bulk and surface changes are accompanied with opposite evolution of apparent activation energy and pre-exponential factor which can be discussed based on a redox mechanism.