The climate change impact associated with greenhouse gas emissions is a major global concern. This work investigates perovskite compounds for oxygen separation from air to supply oxygen to oxyfuel energy systems to abate these significant environmental impacts. The perovskites studied were Me0.5Sr0.5Co0.8Cu0.2O3−δ (MeSCC) where the A-site substitution was carried out by four different cations (Me = Ca, Mg, Sr, or Ba). SEM analysis showed the formation of small particle (<1 µm) aggregates with varying morphological features. XRD analysis confirmed that all compounds were perovskites with a hexagonal phase. Under reduction and oxidation reactions (redox), Ba and Ca substitutions resulted in the highest and lowest oxygen release, respectively. In terms of real application for oxygen separation from air, Ba substitution as BaSCC proved to be preferable due to short temperature cycles for the uptake and release of oxygen of 134 °C, contrary to Ca substitution with long and undesirable temperature cycles of 237 °C. As a result, a small air separation unit of 0.66 m3, containing 1000 kg of BaSCC, can produce 18.5 ton y−1 of pure oxygen by using a conservative heating rate of 1 °C min−1. By increasing the heating rate by a further 1 °C min−1, the oxygen production almost doubled by 16.7 ton y−1. These results strongly suggest the major advantages of short thermal cycles as novel designs for air separation. BaSCC was stable under 22 thermal cycles, and coupled with oxygen production, demonstrates the potential of this technology for oxyfuel energy systems to reduce the emission of greenhouse gases.