A series of poly(fluorenylethynylene)s containing different ratios of perylene bisimide moiety in the backbone were synthesized by Sonogashira cross-coupling reaction. The electron-deficient perylene bisimide moiety was introduced into the backbone to construct the donor-acceptor architectures. The chemical structures of these copolymers were determined by H-1 NMR and FTIR. The solubility, thermal, and optoelectronic properties were studied. The results of UV-vis absorption and fluorescence spectra of these copolymers showed that intramolecular energy transfer and charge separation occur between the fluorenyl alkyne segment and perylene bisimide moiety. (C) 2008 Wiley Periodicals, Inc.