Poly(l-pentyne)s containing biphenyl and phthalimido pendant groups with different spacer lengths {P1(m); -[HC=C(CH2)(3)O-Biph-OCO(CH2)(m)N(CO)(2)C6H4](n)-, Biph=4,4'-biphenylyl; m = 7, 10} are synthesized in satisfactory yields by WCl6-Ph4Sn catalyst in toluene at elevated temperatures. The structures and properties of the polymers are characterized and evaluated by IR, NMR, TGA, DSC, POM, and XRD analyses. Both of the polymers are thermally stable (T-d greater than or less than 300 degrees C) and exhibit nematicity at high temperatures. Their phthalimido groups are converted into amino groups by hydrolysis, which can, after acidification, complex with lead(II) bromide to furnish polyacetylene-perovskite hybrids in high yields. The organic components contribute good solubility to the hybrids, while the perovskite framework induces the polyacetylene chains to align within the inorganic sheets. The hybrids emit a strong UV light of 374 nm upon photoexcitation, whose quantum yield increases with an increase in the spacer length. (c) 2006 Wiley Periodicals, Inc.