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Lewis pairs (LPs) with outstanding performance for nonmetal-mediated catalysis reactions have high fundamental interest and remarkable application prospects. However, their solubility characteristics lead to instability and deactivation upon recycling. Here, the layered porous aromatic framework (PAF-6), featuring two kinds of Lewis base sites (NPiperazine and NTriazine), is exfoliated into few-layer nanosheets to form the LP entity with the Lewis acid. After comparison with various porous networks and verification by density function