Annealing of a side-chain LC polymer (SC-LCP) and a fluorescent dye containing copolymer deposited on friction-transferred PTFE substrates is found to yield macroscopically aligned glassy films. The results obtained by electron diffraction, u.v.-visible and FTi.r. spectroscopy clearly demonstrate that the mesogenic side-groups as well as the fluorescence dye orient with their long axes parallel to the PTFE chain axis. Thus, the SC-LCP aligned thin films adopt a near perfect bookshelf geometry in which the smectic layers are oriented edge-on and perpendicular to the alignment direction. The order parameter P-2 increases from 0.60 to as high as 0.85 when the annealing temperature in the smectic mesophase approaches the smectic to nematic phase transition temperature.