Boron-enriched scaffolds have demonstrated unique features and promising performance in the field of catalysis towards the activation of small gas molecules. However, there is still a lack of facile approaches capable of achieving high B doping and abundant porous channels. Herein, construction of boron- and nitrogen-enriched nanoporous π-conjugated networks (BN-NCNs) was achieved via a facile ionothermal polymerization procedure of hexaazatriphenylenehexacarbonitrile [HAT(CN)6] catalyzed by sodium borohydride. The as-produced BN-NCN scaffolds were featured by high heteroatoms doping (B: up to 23 wt%, N: up to 17 wt%) and permanent porosity (surface area up to 759 m2 g-1). With the B species acting as the active Lewis acid sites and N species acting as the active Lewis base sites, those BN-NCNs delivered attractive catalytic efficiency towards H2 activation/dissociation in both gaseous and liquid phase, performing as efficient metal-free heterogeneous frustrated Lewis pairs (FLPs) catalysts in hydrogenation procedures.