In La1-x Ca (x) Co1-y Fe (y) O-3 perovskites, the calcium substitution modifies the crystalline structure toward a pseudocubic one and produces an electronic unbalance, compensated by the formation of oxygen vacancies and Fe4+ ions. It also increases slightly the ethanol conversion in total combustion, compensating the detriment of catalytic activity caused by the iron substitution and it increases notably the selectivity to total oxidation.