A series of linear thiophene oligomers containing 4, 6, 8, 10, and 12 thienylene units were synthesized and end-capped with naphthalene diimide (NDI) acceptors with the objective to study the effect of oligomer length on the dynamics of photoinduced electron transfer and charge recombination. The synthetic work afforded a series of nonacceptor-substituted thiophene oligomers, T-n, and corresponding NDI end-capped series, TnNDI2 (where n is the number of thienylene repeat units). This paper reports a complete photophysical characterization study of the T-n and TnNDI2 series by using steady-state absorption, fluorescence, singlet oxygen sensitized emission, two-photon absorption, and nanosecond-microsecond transient absorption spectroscopy. The thermodynamics of photoinduced electron transfer and charge recombination in the TnNDI2 oligomers were determined by analysis of photophysical and electrochemical data. Excitation of the T-n oligomers gives rise to efficient fluorescence and intersystem crossing to a triplet excited state that is easily observed by nanosecond transient absorption spectroscopy. Bimolecular photoinduced electron transfer from the triplet states, 3T(n)*, to N,N-dimethylviologen (MV2+) occurs, and by using microsecond transient absorption it is possible to assign the visible region absorption spectra for the one electron oxidized (polaron) states, T-n(+center dot). The fluorescence of the TnNDI2 oligomers is quenched nearly quantitatively, and no long-lived transients are observed by nanosecond transient absorption. These findings suggest that rapid photoinduced electron transfer and charge recombination occurs, NDI-(1)(T)*-NDI -> NDI-(T-n)(+center dot)-NDI-center dot -> NDI-T-n-NDI. Preliminary femtosecond-picosecond transient absorption studies on T4NDI2 reveal that both forward electron transfer and charge recombination occur with k > 10(11) s(-1), consistent with both reactions being nearly activationless. Analysis with semiclassical electron transfer theory suggests that both reactions occur at near the optimum driving force where-Delta G similar to lambda.