The properties of a Langmuir-Blodgett polymeric multilayer film formed from the octadecyl ester of a pentadec-1-ene-maleic anhydride copolymer have been investigated using H-1 wideline and C-13 cross-polarization/magic angle spinning n.m.r. spectroscopy. The spectra indicate that in the multilayer, the polymer chains are disorganized, but are significantly more rigid than in the bulk polymer.