Perovskite-related Ba0.5Sr0.5ZnxFe1−xO3−δ (x = 0, 0.1, 0.2, and 0.3) materials were synthesized via a citric acid–nitrate gel combustion process. The effects of Zn substitution for Fe on the crystal structure, electrical conductivity and sintering ability were investigated. The lattice parameters showed significant increase in cell volume, which is attributed to larger ionic radii of Zn2+ ion. The introduction of Zn2+ promoted the sintering process of Ba0.5Sr0.5ZnxFe1−xO3−δ powders, resulting in both higher density and larger grains. However, the electrical conductivity of this perovskite series decreased dramatically with the increase in the concentration of Zn2+ in the oxides.