We have synthesized and investigated the photophysical properties of a series of electron-donor conjugated copolymers with pendant electron-acceptor units. The copolymers consist of diethynyl-1,4-phenylene, fluorene, or phenylene rings alternating with a phenylene unit bearing a pendant 9,10-anthraquinone moiety. The pendant donor-acceptor polymers were designed to have different optical pi-pi* band gaps, while the oxidation potential of the polymer backbone remains approximately constant in the series. The reduction potential of the donor-acceptor polymers is associated with the pendant acceptor units. This leads to the special situation that the electrochemical gap between oxidation and reduction potentials is constant, while the optical band gap decreases, going from PPP, via PPF, to PPE. This design is used to study the effect of the optical gap on the photoinduced electron-transfer reaction that occurs between the main chain electron donor and the pendant acceptor, while the same polymer architecture and energy of the charge separated state are maintained. Fluorescence and photoinduced absorption spectroscopy are used to study the electron transfer following photoexcitation in relation to solvent polarity and in thin solid films. For the fluorene-phenylene alternating copolymer, intramolecular photoinduced electron transfer occurs in the Marcus optimal region.