Two resorcinarenes and one cavitand having 10-(decylthio)decyl side chains were studied by using both a planar bilayer conductance voltage clamp device and a Langmuir trough. The former detects the presence of pore formation in a phospholipid bilayer and the latter probes the aggregation behavior of the amphiphiles as a monolayer. The Langmuir trough behavior of these amphiphiles showed that higher polarity head groups dominated organization, but as the head group polarity decreased, monolayer organization was dominated by the four side chains. Among the three, i.e., resorcinarene, octamethyl resorcinarene, and cavitand, only the methylated head group derivative formed ion-conducting pores in bilayers.