Highly ordered densely crosslinked liquid crystalline poly(vinyl ether) films have been prepared by in situ photopolymerization of oriented bifunctional mesogenic vinyl ether monomers. Orientation was achieved by a simple surface treatment, using a unidirectionally rubbed polyimide film. Polymerization from various monomer phases resulted in LC polymer network films with different molecular organizations. The films were analyzed with small-angle x-ray scattering, polarized light microscopy and infrared-dichroism measurements. It was shown that films with nematic, smectic A and smectic B structures were obtained, the latter having a very high degree of orientation.