Reversible regulation of membrane microstructures via non-covalent interactions is of considerable interest yet remains a challenge. Herein, we discover a general one-step approach to fabricate supramolecular porous polyelectrolyte membranes (SPPMs) from a single poly(ionic liquid) (PIL). The experimental results and theoretical simulation suggested that SPPMs were formed by a hydrogen-bond-induced phase separation of a PIL between its polar and apolar domains, which were linked together by water molecules. This unique feature was capable of modulating microscopic porous architectures and thus the global mechanical property of SPPMs by a rational design of the molecular structure of PILs. Such SPPMs could switch porosity upon thermal stimuli, as exemplified by dynamically adaptive transparency to thermal fluctuation. This finding provides fascinating opportunities for creating multifunctional SPPMs.