A series of pi-conjugated oligomer-acceptor dyads were synthesized that feature oligo(phenylene ethynylene) (OPE) conjugated backbones end-capped with a naphthalene diimide (NDI) acceptor. The OPE segments vary in length from 4 to 8 phenylene ethynene units (PEn-NDI, where n = 4, 6 and 8). Fluorescence and transient absorption spectroscopy reveals that intramolecular OPE -> NDI charge transfer dominates the deactivation of excited states of the PEn-NDI oligomers. Both charge wseparation (CS) and charge recombination (CR) are strongly exothermic (Delta G degrees cs similar to -1.1 and Delta G degrees(CR) similar to -2.0 eV), and the driving forces do not vary much across the series because the oxidation and reduction potentials and singlet energies of the OPEs do not vary much with their length. Bimolecular photoinduced charge transfer between model OPEs that do not contain the NDI acceptors with methyl viologen was studied, and the results reveal that the absorption of the cation radical state (OPE-center dot) remains approximately constant (lambda similar to 575 nm) regardless of oligomer length. This finding suggests that the cation radical (polaron) of the OPE is relatively localized, effectively occupying a confined segment of n <= 4 repeat units in the longer oligomers. Photoinduced intramolecular electron transfer dynamics in the PEn-NDI series was investigated by UV-visible femtosecond transient absorption spectroscopy with visible and mid-infrared probes. Charge separation occurs on the 1-10 ps time scale with the rates decreasing slightly with increased oligomer length (beta(CS) similar to 0.15 angstrom(-1)). The rate for charge-recombination decreases in the sequence PE4-NDI > PE6-NDI similar to PE8-NDI. The discontinuous distance dependence in the rate for charge recombination may be related to the spatial localization of the positive polaron state in the longer oligomers.