The recovery of valuable metals from spent Li–ion batteries (LIBs) and their full utilization has become essential to support sustainable development. Herein, we designed an efficient 3D porous Co–N–C catalyst (Co@NCW–4) by combining the Co recovered from spent LIBs with biomass. Results illustrate Co@NCW–4 with the porous lamellar architecture utilizes the multiple channel structure for effective mass transfer and provides plentiful active sites, thus exhibiting great bifunctional oxygen electrocatalytic activity and stability. According to the data, Co@NCW–4 has the half–wave potential of 0.823 V vs RHE for oxygen reduction reaction, and an overpotential of 350 mV at 10 mA cm−2 for oxygen evolution reaction. The rechargeable Zn–air batteries assembled with the Co@NCW–4 exhibit excellent power density of 215 mW cm−2, and long–term stability better than RAZBs of benchmark Pt/C + RuO2. This research represents a general method for converting abundant biomass and spent LIBs into high environmentally preferable materials for energy–related applications.