Polynorbornenes substituted with 1-cyano-2-naphthyl and 2,5-dicyanophenyl groups as accepters and terminated with pyrene as donor have been prepared by ring-opening metathesis polymerization. When excited with monochromatic light, pyrene transfers an electron, producing a radical ion pair with concurrent reduction of the acceptor. In the copolymers with one acceptor block, steady-state emission spectra reveal extensive pyrene fluorescence quenching and exciplex formation between the pyrene and the acceptor. In copolymers with two acceptor blocks, the steady-state emission spectra reveal two intramolecular exciplexes assigned to the cyanonaphthalene-pyrene and dicyanobenzene-pyrene excited-state complexes. Transient absorption spectra display an overlap of the pyrene triplet-triplet and radical cation spectra for all of the polymers. The Lifetimes of the transient absorption maxima are dependent upon the identity of the acceptor and the length of the acceptor block.