The main barrier for gas permeation across ionically cross-linked Langmuir-Blodgett (LB) bilayers, made from a 5,11,17,23,29,35-hexakis[( N, N, N-trimethylamonium)-N-methyl-37,38,39,40,41,42-hexakis-n-hexamedecyloxy-calix[6]arene hexachloride (1) and poly(sodium 4-styrenesulfonate) (PSS), has been determined by measuring the effects of NaCl on the thickness of the PSS layer encased between the calixarene layers and the permeation characteristics of the resulting membrane. Specifically, the fact that NaCl increases the uptake of PSS by the LB film and increases the permeance of these membranes toward N2 and CO2 but not He provides compelling evidence that the main barrier for permeation is the calixarene layers and not the PSS layer that is encased between them. The effects of NaCl on ionic cross-linking, surface pressure, and surface viscosities are discussed.