Carboxyl and amino groups have been inserted into calix(8)arene rings in order to yield two materials which, when processed as alternate layer Langmuir-Blodgett assemblies, exhibit the pyroelectric effect. Such a temperature-dependent electric polarization arises partially from proton transfer between the acid and amine groups. The calix(8)arene system has been selected owing to the extreme thinness of each monolayer (similar to 1.0 nm), the resulting high density of acid-amine pairs and the very high thermal stability exhibited by calixarenes (typically mp > 200 degrees C).