Polymers containing liquid crystal groups have been studied previously as waveguides, and they have been deposited as spacer materials with various chromophores to form alternating films However, only a few members of this group of materials have been studied in any detail, and very little structural information has been obtained so far. Therefore, a more detailed examination of these materials as mono-and multilayers was undertaken. A new group of materials including the same mesogenic group, polymeric sulfones, was also studied. The polymers gave steep isotherms with high collapse pressures, indicating good packing of the monolayers, and could be deposited to form thick multilayers. X-ray diffraction showed that an ordered multilayer was formed, and the effects of the polymers chemical nature on the structure of the LB films are discussed. It appears that the dominant factor in monolayer structure is the nature of the polymer backbone rather than that of the liquid crystal side chains, which play a secondary role.