Calix-4-resorcinarenes form multilayers (7-40 layers) by self-assembly from hydrophobic solvents such as hexane on various substrates. Hydrophilic solvents such as ethanol reverse this process. Infrared and X-ray photoelectron spectroscopy, together with X-ray and neutron reflectometry measurements are described. Comparison is made with similar measurements on Langmuir-Blodgett films of these materials. The aim of this work was to study the structure and morphology of the multilayers in the context of a model which has been proposed for their bilayer structure and which is based on the X-ray crystal structure of calix-4-resorcinarene 1. These multilayers have been found to bind glutaric acid selectively.