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Synthesizing large-area ultrathin two-dimensional (2D) nanostructures in aqueous media has received considerable increasing attention but remains a big challenge.Herein,we report a facile method for the synthesis of two unprecedented large-area ultrathin 2D supramolecular nanosheets via ionic self-assembly in water.Upon consideration of electrostatic interaction and repulsive effect,deprotonated tetrakis(4-carboxyphenyl)porphyrin (TCPP) or Fe(lll) tetra(4-carboxyphenyl)porphine chloride (TCPP(Fe)) as connection vertex and protonated bis(2-dimethylaminoethyl) ether (BDMAEE) unit as bridging edge connect with each other to form few-layer 2D nanosheet with a thickness of ～ 1.8-1.9 nm,while the lateral size can close to one hundred micrometers.Moreover,the well-dispersed 2D TCPP(Fe)-BDMAEE with heme-like active center displays intrinsic peroxidase-like catalytic activity,which can be used to detect hydrogen peroxide.The present facile strategy highlights new opportunities in constructing large-area ultrathin 2D supramoleoular nanomaterials and paves the avenue to expand their potential applications.