A laminated thin-film composite (TFC) membrane system consisting of an ultrafiltration support, an ordered, nanoporous, polymerized lyotropic liquid crystal (LLC) intermediate layer, and an ultrathin, dense polydopamine top layer was developed for use as a "breathable" chemical-protective garment material. These membranes exhibit a high water vapor transport rate (ca. 500 g m(-2) day(-1)) and excellent rejection of both CEES (a blister agent simulant) and DMMP (a nerve agent simulant) vapors under ambient conditions. The (water:CEES) and (water:DMMP) molar vapor selectivity values of this new composite membrane system were found to be 170 +/- 40 and >3400, respectively, which exceed those of any previously reported LLC-based membrane system.