The alignment of six fluorescent materials (p-terphenyl, p-quaterphenyl, p-quinquephenyl, diphenylstilbene, 1,4-bis(2-methylstyryl)benzene, and 1,4-bis-2-(5-phenyloxazolyl)benzene) grown from the vapour phase on to friction-deposited, highly oriented poly(tetrafluoroethylene) (PTFE) films was studied. The dichroic ratio of the fluorescent films produced was determined by polarized spectroscopic fluorescence measurements, and the crystallographic orientation of these materials was determined by transmission electron microscopy. The measured dichroic ratios ranged from 1.7 for diphenylstilbene to 5.0 for the p-quaterphenyl film. Electron diffraction patterns revealed that five of the fluorescent materials grew epitaxially on the single crystal-like PTFE films, the fluorescent crystals adopting particular orientations with respect to the crystallographic planes of PTFE. On the other hand, crystals of 1,4-bis-2-(5-phenyloxazolyl) benzene aligned in a fibre pattern, apparently by a grapho-epitaxial mechanism.