The oxygen content was measured in cubic perovskite-type La1/3Sr2/3Fe1-xMnxO3-δ (x = 0.1, 0.17, 0.25, and 1/3) in the range of oxygen partial pressure from 10-22 to 0.5 atm at 750-950 °C with a step of 50 °C by coulometric titration. Gradual removal of oxygen from the oxides during the measurements was carried out until the stability limit was achieved and the reductive decomposition began. An increase in manganese content was shown to lead to a decrease in the stability of La1/3Sr2/3Fe1-xMnxO3-δ under reducing conditions. The obtained data on oxygen content were used for defect chemistry modeling in the oxides. The enthalpy of the Fe3+ to Fe4+ and Mn3+ to Mn4+ oxidation reactions (ΔHox0) was determined to be -103.2 ± 0.3 and -250 ± 2 kJ mol-1, respectively, for the x = 0.1 composition, and increased slightly with increasing manganese content. The large difference in ΔHox0 determines a strong distinction between the behavior of iron and manganese in perovskite-type oxides. An increase in manganese content in La1/3Sr2/3Fe1-xMnxO3-δ was found to lead to a decrease in the concentration of Fe4+ ions, but did not affect the concentration of Fe2+ ions. The impact of La/Sr ratio was evaluated by comparison of the obtained data with that for La0.5Sr0.5Fe1-xMnxO3-δ, and found to be different for iron and manganese. An increase in lanthanum fraction causes a decrease in the concentration of Fe2+ ions and an increase in the concentration of Mn2+ under reducing conditions.