The oxygen non-stoichiometry was determined by coulometric titration for the perovskite oxides La0.2Sr0.8FeO3−δ and La0.2Sr0.8Fe0.8B0.2O3−δ (B = Ti4+ and Ta5+) in the temperature range 600 ◦C ≤ T ≤ 900 ◦C and the oxygen partial pressure range: 1 · 10−15 ≤ pO2 ≤ 0.209 atm. The non-stoichiometry (δ) is observed to decrease with B-site substitution of Fe. The data can be well fitted with simple defect chemistry models. At low oxygen non-stoichiometry all compositions show a deviation from a localized electrons defect model. The standard and partial molar thermodynamic quantities were obtained and a gradual transition from localized to itinerant electrons with decreasing non-stoichiometry is proposed from the δ-dependency of the configurational entropy. The absolute value of the enthalpy of oxidation decreases upon B-site substitution of Fe proposing a decreased thermodynamic stability for the substituted materials. The electrical conductivity was measured at T = 900 ◦C in the oxygen partial pressure range: 1 · 10−17 ≤ pO2 ≤ 0.209 atm. The electrical conductivity and charge carrier mobility decrease upon 20% substitution of Fe roughly by a factor of 2, but do not show a significant dependence on the nature of the B-site dopant.