We report the studies of the molecular conformation and chain orientations through characterization of the vibrational modes in crystalline Langmuir–Blodgett films of the polyvinylidene fluoride/trifluoroethylene copolymer. The infrared spectra obtained by polarized reflectometry and ellipsometry showed that the ferroelectric phase has predominantly all-trans conformation and the paraelectric phase has predominantly alternating trans-gauche conformation, as in solvent-formed films of the same copolymer. The results showed that the polymer chains are predominantly parallel to the film plane with a random in-plane orientation and most of the ferroelectric phase vibrational mode behaviors are consistent with the published mode assignments. The...