Highly oriented luminescent films are produced by stretching a 30-mu m-thick polyvinyl alcohol matrix doped with water-soluble polyrotaxanes and their unthreaded analogues. Photoluminescence experiments reveal that over 95% of the emitted light is polarized along the orientation direction. A hybrid organic-inorganic light-emitting diode is built to investigate the possibility of using these films as polarizing filters for solid-state lighting and display technology.