A pressure swing adsorption system for processing an oxygen-containing feed gas mixture to extract oxygen therefrom, comprising an adsorbent bed arranged for elevated temperature sorption/desorption operation, wherein the adsorbent bed comprises a ceramic adsorbent having affinity for oxygen when the ceramic adsorbent is at elevated temperature. Suitable ceramic adsorbents include lanthanum calcium cobalt ferrites and other oxygen ionic transport ceramic metal oxide compositions. As applied to the separation of air or other oxygen/nitrogen mixtures, the PSA system is effective to produce oxygen-rich as well as nitrogen-rich product gases.