Refined architectures are of vital importance in determining the electrocatalytic activity of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, pyridinic NB pair doped carbon microspheres (NB-CMS) with hierarchical micropore-mesopore structure are prepared via a SiO2 hard template assisted CO2 activation strategy. The pyridinic NB pair accounts for ≈ 59.9 % of all N species in NB-CMS, accelerating the ORR process with onset potential (0.996 V) and half-wave potential (0.889 V). Meanwhile, the NB-CMS also exhibits high OER performance with overpotential of 384 mV at 10 mA cm−2. The assembled Zinc-air battery exhibits maximum power density of 134 mW cm−2 and long-term charging and discharging stability over 358 h. Density functional theory (DFT) simulations reveal that the pyridinic NB pair exhibits the highest electrocatalytic performance in dual-functional catalysis, owing to the highest charge density and readily accepts electrons from *OOH adsorbate of N active site neighboring B.