The presence of charge transfer states generated by the interaction between the fullerene acceptor PCBM and two alternating copolymers of fluorene with donor-acceptor-donor comonomers are reported; the generation leads to modifications in the polymer bandgap and electronic structure. In one of polymer/fullerene blends, the driving force for photocurrent generation, i.e., the gap between the lowest unoccupied molecular orbitals of the donor and acceptor, is only 0.1 eV, but photocurrent is generated. It is shown that the presence of a charge transfer state is more important than the driving force. The charge transfer states are visible through new emission peaks in the photoluminescence spectra and through electroluminescence at a forward bias. The photoluminescence can be quenched under reverse bias, and can be directly correlated to the mechanism of photocurrent generation. The excited charge transfer state is easily dissociated into free charge carriers, and is an important intermediate state through which free charge carriers are generated.