Calix[4]resorcinarenes octafunctionalized with methyl alpha-acetate (CALES) or methyl alpha-acetamide (CALAM) have been used to form Langmuir-Blodgett (LB) films on several different substrates. Spectroscopic characterization of these species as solids, solutions, and LB films were carried out using FT-IR, FT-Raman, UV-visible, and fluorescence spectroscopies. Considering the spectroscopic evidence, the conformation of both CALES and CALAM in the LB films was found to be the flattened cone. It has been shown that the presence of metal cations in the subphase results in incorporation of cations into the LB film. The film organization of the octafunctionalized calix[4]resorcinarene in the film is determined by the metal cation.