HighlightsJUC-610-nanosheet exhibits highly efficient oxygen reduction reaction (ORR) catalytic activity in alkaline electrolyte with half-wave potential of 0.72 V versus reversible hydrogen electrode, which is one of the best covalent organic frameworks (COF)-based ORR electrocatalysts reported so far.It has been confirmed by experiments and density functional theory calculations that the abundant electrophilic structure in Q3CTP-COFs induces a highly density of carbon active sites, and the unique bilayer stacking facilitates the exposure of active carbon sites and accelerates the mass diffusion during ORR.JUC-610-nanosheet can also serve as a promising cathode for Zn-air batteries (power density of 156 mW cm–2at 300 mA cm–2), which promotes the development of metal-free carbon-based electrocatalysts.