Poly(1-phenyl-1-octyne)s containing different stereogenic and chromophoric pendants {-[(C6H13)C= C(C6H4-p-CO2-R)] n -R = [(1S)-endo]-(?)-borneyl (P3), (1R,2S,5R)-(?)-menthyl (P4), -C6H4-p-(1R,2S,5R)-(?)-menthyl (P5), 2-napthyl (P6), 4-biphenylyl (P7)} have been designed and synthesized. The polymers are prepared in moderate yields by WCl6-Ph4Sn and possess high molecular weights (M w up to 64000). The structures and properties of the polymers are characterized and evaluated by NMR, TGA, UV, CD, PL, and EL analyses. All the polymers are thermally stable and their temperatures for 5% weight loss locate in the range of 300 to 416°C under nitrogen. The energy band gaps of all the polymers are ~3.0 eV. Polymers P4 and P5 show CD absorptions associated with the helicity of the polymer segments. Excitation of the THF solutions of P3–P7 by UV irradiation gives strong blue lights of ~485 nm with quantum yields higher than 20%. The thin films of the polymers also emit in the same spectral region, indicative of little aggregation-caused quenching of light emission. Multilayer EL devices with a configuration of ITO/Polymer:PVK/BCP/Alq3/LiF/Al are constructed, which emit blue lights of ~487 nm. The maximum luminance and external quantum efficiency vary with the pendant groups, with P6 exhibiting the highest external quantum efficiency of 0.16%. The spectra stability of the EL devices is outstanding and the EL peak maximum experiences little change with the applied voltage.