Oxygen is experimentally known to be incorporated in acceptor-doped perovskites at high temperatures, leading to a hole conductivity proportional to p 1/4 O2 and increasing with temperature [ 1 2O2 + V ** O → OXO + 2h *]. Either this high-temperature incorporation is thermodynamically favored by temperature, suggesting an endothermic process ( H0 > 0), or it is exothermic. In the latter case, since it is obviously associated with a S0 < 0, the process should be favorable only at low temperatures, except if kinetically blocked. To examine this phenomenon, the reaction ofO2 incorporation into the acceptor-doped perovskites BaSnO3 and BaZrO3, doped by trivalent dopants (Ga, Sc, In, Y), according toBaSn/Zr1−xMxO3−x/2 + x/4O2 → BaSn/Zr1−xMxO3, is studied by density-functional calculations for a high dopant concentration (x = 0.25). In this process, the charged vacancies V ** O resulting from the charge compensation produced by doping, are filled with oxygen atoms, yielding a metallic compound with holes. It is found to be exothermic in all cases, showing that these acceptor-doped perovskites are able to incorporate oxygen at low temperatures, whereas the reaction is unfavorable above a given temperature, whose value is discussed. At any rate, it is suggested that the process is kinetically blocked at low temperatures due to very slow thermally activated vacancy diffusion. A thermochemical approach is presented that tentatively explains why the hole conductivity increases with temperature at high temperatures, although the hole concentration decreases, yielding a model compatible with experimental observations and theoretical calculations.