Highly-oriented films of insoluble polymers, such as poly(dimethylsilylene) and poly(p-phenylene), on smooth substrates were prepared by the friction deposition technique. The structures of films were characterized by polarized light microscopy, transmission electron microscopy, and polarized ultraviolet-visible light absorption spectroscopy to confirm the uni-directional molecular orientation. Especially, polarized fluorescence spectroscopy revealed highly-polarized photoluminescence from the oriented films.