Nanoporous membranes prepared by supramolecular assembly of block copolymers have attracted increasing attention for their well-defined nanostructure, adjustable pore size, and large-scale manufacturing. In this context, the development of nanoporous membranes with tailored surface chemistry and specific functionalities presents significant opportunities and is critical for their practical applications. Herein, we demonstrate an efficient supramolecular approach for fabricating arginine-functionalized multifunctional nanoporous membranes by assembling the conventional polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) with the designed arginine-based amphiphile containing three terminal pyrrole moieties (Py-3-Arg) that could be polymerized to form the stable membranes in organic solvents followed by the removal of PS-b-P4VP template. Because of the distinct chemical properties of arginine moieties decorated on the wall surface, the obtained nanoporous membranes exhibit multifunctionality and hold a broad scope of promising applications, including but not limited to pH-tunable gating, selective adsorption, and membrane catalytic capability.