<p>Developing materials with both efficient CO₂ capture and catalytic conversion functions is of vital importance for realizing carbon recycling. Among various options, Frustrated Lewis Pairs (FLPs), a metal-free catalytic system with great potential, still face a significant obstacle: precisely and densely building FLPs active sites within solid supports. To tackle this issue, this research puts forward a novel B-N covalent bond template-locking approach. We selected covalent organic frameworks (BNOF), which already have B-N covalent bonds in skeletons, as starting materials. Through a programmed carbonization process, we successfully synthesized a series of porous carbons (BNOF-PCs) with in-situ and adjacent B and N co-doping. Comprehensive characterization indicated that this method allowed BNOF-PCs to retain the rich porous structure of BNOFs. More importantly, the negative shift in the B 1s binding energy combined with the positive shift in the N 1s binding energy directly proved the electron synergy between B and N atoms used to constructed FLPs active centers. In terms of performance, the prepared materials performed outstandingly in both CO₂ capture and cycloaddition reactions. For instance, BNOF-750 had a CO₂ adsorption capacity of 47 cm³·g^− 1, and its adsorption mechanism could be adjusted by temperature. BNOF-850 could catalyze reactions between different epoxides and CO₂ with a yield of up to 99% and could be recycled stably at least six times.</p> Graphical Abstract <p></p>