The Langmuir-Blodgett (LB) alternate layer fabrication technique provides one of the most effective methods to fabricate organic thin films in the nanoscale. The structure of these thin films could be controlled at the molecular scale by spreading a monolayer on an air-water interface followed by sequential transferring of this layer onto a selected solid substrate. These films can be utilized within optical, electrical and biological applications in many different fields. Within this paper, two calixarenes containing either carboxylic acid or amino substituents were utilised to prepare multilayer LB films and to study the electrical characteristic of these films using I-V and C-f measurements. The resultant calixacid/amine multilayers demonstrated a highly non-linear I-V behaviour which obeys a Schottky conduction mechanism.