Homeotropically oriented layers and films of liquid crystals especially on polymeric substrates. The layers and films, which also can be multi-layered films comprising a homeotropically aligned anisotropic film, are preparable by application of an orientation layer to the substrate. The orientation layer can be either an organic surfactant which is fixed in a matrix of a polymeric material or an inorganic thin layer such as aluminum or Al.sub.2O.sub.3.