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The creation of A-site cation defects within a perovskite oxide can substantially alter the structure and properties of its stoichiometric analogue. In this work, we demonstrate that by vacating 2 and 5% of Asite cations from SrNb0.1Co0.9O3-δ (SNC1.00) perovskites (Sr1-sNb0.1Co0.9O3-δ,s = 0.02 and 0.05; denoted as SNC0.98 and SNC0.95, respectively), a Jahn–Teller (JT) distortion with varying extents takes place, leading to the formation of a modified crystal lattice within a the perovskite framework. Electrical conductivity, electrochemical performance, chemical compatibility and microstructure of Sr1-sNb0.1Co0.9O3-δ as cathodes for solid oxide fuel cells were evaluated. Among SNC1.00, SNC0.98 and SNC0.95, SNC0.95 (P4/mmm symmetry (#123)) which exhibits a large JT distortion in conjunction with charge-ordering of cobalt (Co) shows the best oxygen reduction reaction (ORR) activity at low temperature while SNC0.98 (P4mm symmetry (#99)), which displays a local JT distortion, shows the poorest performance.