Abstract Fabricating nanoscale assemblies that can respond to gas signaling molecules has emerged as a field of growing interest owing to their unique biomedical applications in gas‐guided delivery and gas therapeutics. Yet, among a variety of endogenous gaseous biosignals, exploiting sulfur dioxide (SO 2 ) as a cue for controllable self‐assembly remains elusive, despite its crucial two‐sided roles both in physiology and pathology. Here we show a SO 2 ‐responsive polymersome system assembled from a novel class of cyanine‐containing block copolymers. By intake of SO 2 gas, the tautomerism of cyanine drives such vesicles to continuously deform, and change into long nanotubes through axial stretching and anisotropic extrusion of the membranes. Unexpectedly, during this order‐to‐order phase transition, their membranes manifest well SO 2 ‐dose‐dependent permselectivity, which allows the cargos of different sizes loaded therein to be selectively transferred across the bilayers. This study would inspire us to better understand and mimic the function of gas signaling molecules in shifting biomembrane shape and managing transmembrane traffic.