Developing bifunctional catalysts that increase both the OER and ORR kinetics and transport reactants with high efficiency is desirable. Herein, micro‑meso-macroporous FeCo-N-C-X (denoted as “M-FeCo-N-C-X”, X represents Fe/Co molar ratio in bimetallic zeolite imidazole frameworks FeCo-ZIFs) catalysts derived from hierarchical M-FeCo-ZIFs-X was prepared. The micropores in M-FeCo-N-C-X have strong capability in O2 capture as well as dictate the nucleation and early-stage deposition of Li2O2, the mesopores provided a channel for the electrolyte wetting, and the macroporous structure promoted more available active sites when used as cathode for Li-O2 batteries. More importantly, M-FeCo-N-C-0.2 based cathode showed a high initial capacity (18,750 mAh g−1@0.1 A g−1), good rate capability (7900 mAh g−1@0.5 A g−1), and cycle stability up to 192 cycles. Interestingly, the FeCo-N-C-0.2 without macropores suffered relatively poorer stability with only 75 cycles, although its discharge capacity was still as high as 17,200 mAh g−1(@0.1 A g−1). The excellent performance attributed to the synergistic contribution of homogeneous Fe, Co nanoparticles and N co-doping carbon frameworks with special micro‑meso-macroporous structure. The results showed that hierarchical FeCo-N-C architectures are promising cathode catalysts for Li-O2 batteries.