Perylene (Py)-containing polyacetylenes with different skeleton structures -[HC=C(C6H4)CO2-Py](n)-(P1), -[HC=C(CH2)(8)CO2-Py](n)-(P2), and -{[(C6H5) C=C(CH2)(9)NH2]-co-[(C6H5)C=C(CH2)(9)-Py]}(n)- (P3) are synthesized in satisfactory yields by Rh-catalyzed polymerization (for P1 and P2) and polymer reaction (for P3). All the polymers are soluble and possess high molecular weights (M-w up to 2.8 x 105). Their structures and properties are characterized and evaluated by IR, NMR, UV, TGA, PL, and photovoltaic (PV) analyses. The polymers are thermally stable, losing little of their weights when heated to 330 degrees C. When their solutions are irradiated, their perylene pendants emit intense red fluorescence at 610 nm. PV cells with a configuration of ITO/PEDOT:PSS/polymer/LiF/Al are fabricated, which show maximum current density of 10.3 mu A/cm(2). The external quantum efficiency is sensitive to the polymer structure, with P3 exhibiting the highest value of 0.23%. (C) 2008 Wiley Periodicals, Inc.