An alignment structure useful in a liquid crystal display device comprising a substrate having disposed thereon an oriented film of a lyotropic nematic liquid crystalline material. Particularly useful lyotropic materials include a class of nematic liquid crystalline compounds known as chromonics. The substrates can be made by coating the lyotropic liquid crystal material onto the substrate to provide an oriented film of the lyotropic material. The alignment structure can also include one or more polarizing dyes or other additives and can thus be made to perform polarizing, retarding and/or color filtering functions in addition to alignment and orientation functions. Optical devices containing such alignment structures and methods of making such devices are also described.