The development of robust and efficient electrocatalysts for use in fuel cells and metal–air batteries has garnered a great deal of interest due to the quest for clean and renewable energy sources. In this paper, a promising Co-doped Pr0.5Ba0.4Ca0.1Fe1-xCoxO3-δ (x = 0, 0.2, 0.4, 0.6, 0.8; denoted as PBCFC-x, x = 0, 2, 4, 6, 8) with enhanced durability and electrocatalytic ORR/OER activity for zinc–air battery cathode catalysts is presented. Particularly, PBCFC-6 exhibits the best bifunctional catalytic activity in alkaline media among several materials, according to research using the RDE. The zinc–air battery with PBCFC-6 as the cathode catalyst delivered the smallest discharge–charge voltage difference at the current density of 10 mA·cm−2 and only increased by 0.031 V after 220 cycles (220 h), demonstrating its superior bifunctional catalytic activity and durability. The optimized electrochemical performance of both OER and ORR as well as stability in zinc–air batteries might result from the higher electrical conductivity, increasing concentration of adsorbed oxygen, and the greater proportion of Fe4+ (t2g3eg1) with optimal electron occupancy, owing to the partial replacement of Fe with Co
