The ionic cross-linking (i.e., "gluing") of a Langmuir-Blodgett bilayer derived from a cationic calix[6]-arene has been found to be strongly dependent upon the concentration of poly(4-styrenesulfonate) that is present in the subphase; that is, relatively high concentrations favor low monolayer viscosities at the air-water interface, good Langmuir-Blodgett transferability, and high-quality bilayers. A model that accounts for this behavior is presented.