A vibrational characterization of C-undecylcalix[4]resorcinarene (CALOL) has been carried out. The first Raman data of CALOL obtained with near-infrared excitation at 1064.1 nm are reported. The infrared spectra were also recorded, and characteristic fundamental frequencies have been assigned. These data identify two possible point groups, C-4v and C-2v, for CALOL in the solid state. The formation of stable Langmuir monolayers and the surface pressure versus molecular area (pi-A) isotherms were found to be dependent upon spreading solvent and temperature. Langmuir-Blodgett films of CALOL transferred from a chloroform solution onto quartz show clearly different electronic properties compared to films obtained from toluene solution. The conformational distribution of CALOL in bulk solutions and the stabilization of conformers in Langmuir-Blodgett films are discussed.