LaMn0.5Mg0.5O3.y MgO and LaCr0.5-xMnxMg0.5O3.y MgO catalysts (x=0-0.25, y=0-17) were prepared, characterized (XRD, BET, SEM-EDS, TEM, FTIR, chemical and atomic absorption analyses), tested for high-temperature methane combustion and aged in presence of SO, to investigate sulfur effect on catalytic activity. Different roles of manganese and chromium in the perovskite structure have been assessed: (i) manganese improves the activity of catalysts in the fresh state, whereas chromium worsens it; (ii) owing to its basic nature, manganese makes perovskites more prone to adsorb SO, and so less resistant to sulfur poisoning, whereas chromium, owing to its acidic nature, has opposite effects; (iii) the partial solubility of chromium oxide in basic media renders Cr-catalyst regeneration by NH3 leaching less effective. MgO promotes catalytic activity of fresh LaCr0.5Mg0.5O3.y MgO catalysts and slows down sulfur poisoning of LaMn0.5Mg0.5O3.y MgO and LaCr(0.25)Mn(0.25)Mg(0.5)O(3)(.)17 MgO catalysts only.