Four poly(oxadiazole-imide)s containing naphthalene rings, with different flexibility and molecular weight, are investigated with respect to their rheological properties to establish the optimal processing conditions from solution phase to film state for liquid crystal orientation purposes. The film uniformity and strength are determined by monitoring the flow behavior and chain entanglements. The solution rheological data are in agreement with film tensile testing, revealing that higher molecular weight favors chain entanglements and implicitly the film mechanical resistance. In order to analyze the suitability of these films as alignment layers their surface is patterned by rubbing with two types of velvet. Liquid crystal alignment of 4'-pentyl-4-biphenylcarbonitrile nematic is tested by polarized light microscopy. The resulting behavior is correlated with the polyimide malleability and characteristics of the textile fibers, namely their polarity, size, and mechanical features. The competitive effects between chain flexibility and entanglements, together with the interactions occurring between the polymer and velvet are analyzed in order to explain the surface regularity, which influences the uniformity of the liquid crystal alignment. The contrast between dark and bright states recorded on the liquid crystal cell indicates that some of these polynaphthalimides are promising candidates for liquid crystal display devices.