This work investigates the partial substitution of yttrium in place of iron in BSCF to form Ba0.5Sr0.5Co0.8Fe0.2−xYxO3−δ, where x varied between 0 and 0.2. X-ray diffraction patterns showed the formation of a perovskite cubic phase structure up to x = 0.15, whilst the full substitution of yttrium (x = 0.2) for iron resulted in a non-cubic crystal structure that did not exhibit oxygen permeation. The yttrium partial substitution in BSCFY discs (1.2 mm thick) delivered best results for x = 0.025, as oxygen fluxes reached 2.05 ml cm−2 min−1 at 900 °C, an increase of 160% as compared to a blank BSCF (x = 0) membrane. This was attributed to the combined effect of the formation of a greater number of oxygen vacancies, together with improved ion mobility, associated with the beneficial yttrium substitution into the BSCF perovskite structure which stemmed from the crystal lattice expansion.