This invention belongs to the field of protonceramic electrochemical battery technology, and discloses a cobalt-free air electrode material for a reversible proton conductor type ceramic electrochemical battery, its preparation, and its application. The air electrode material has PrBa 0.8‑x Ca 0.2 Fe 1.8 Ce 0.2‑y O 6‑δ The three-phase structure of BaCeO3 and CeO2 forms BaCeO3 and CeO2 nanoparticles attached to PrBa 0.8‑x Ca 0.2 Fe 1.8 Ce 0.2‑y O 6‑δ Heterogeneous structure on the surface of the skeleton; where 0