All-solid-state zinc–air pouch cells promise high energy-to-cost ratios with inherent safety; however, finding earth-abundant high power/energy cathodes and super-ionic electrolytes remains a fundamental challenge. Here we present realistic zinc–air pouch cells designed by the (101)-facet copper phosphosulfide [CPS(101)] as a cathode as well as anti-freezing chitosan-biocellulosics as super-ionic conductor electrolytes. The proposed CPS(101) exhibits trifunctional activity and stability (>30,000 cycles) towards reversible oxygen reactions and hydrogen evolution reactions, outperforming commercial Pt/C and RuO2. Furthermore, hydroxide super-ion conductors utilizing polymerized chitosan-biocellulosics reveal exceptional conductivity (86.7 mS cm−1 at 25 °C) with high mechanical/chemical robustness. High cell-level energy densities of 460 Wh kgcell–1/1,389 Wh l−1 are normally measured in pouch cells (1 Ah) with a cycle lifespan of 6,000/1,100 cycles at 25 mA cm−2 for 20/70% depths of discharge, and the highest densities we could achieve were 523 Wh kgcell–1/1,609 Wh l−1. Flexible pouch cells operate well at rates of 5–200 mA cm−2 over a broad temperature range of −20 to 80 °C.