Room temperature engineered spatially connected p-type double perovskite oxide (BaPrMn_1.75Co_0.25O_5+δ, BPMC) nanosheets (NSs) with n-type nitrogen-doped multi-walled carbon nanotubes (NCNTs) show significant enhancement in bifunctional oxygen electrocatalytic activity. The optimization of the donor level by charge transfer from the perovskite to NCNTs is demonstrated to be a prodigious approach to facilitate redox oxygen activation. A proof-of-concept rechargeable zinc–air battery (ZAB) with BPMC containing a 10 wt% NCNT (BPMC/NCNT-10) cathode demonstrates the highest specific discharge capacity of 789.2 mA h g_Zn⁻¹ and cyclic stability for 85 h at a current density of 5 mA cm⁻².