Amphiphilic calix[4]resorcinolarenes (C[4]RA) with different hydrocarbon chains have been synthesized. The self-assembling properties of the C[4]RA molecules on the water surface were studied by Pi-A and phi-A diagram measurements. Langmuir-Blodgett (LB) films of these compounds were produced. Complexing properties of C[4]RA LB films were investigated by the quartz-crystal balance method and ellipsometry. Different adsorption mechanisms were found for water and aromatic molecules.