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The improved photovoltaic performance of narrow band gap polymer:fullerene solar cells processed from solutions containing small amounts of 1,8-octanedithiol is analyzed by modeling of the experimental photocurrent. In contrast to devices that are spin coated from pristine chlorobenzene, these cells do not produce a recombination-limited photocurrent. Modeling of the experimental data reveals that a sixfold reduction in the decay rate of photogenerated bound electron–hole pairs can account for the marked increase in short-circuit current density and fill factor. At short-circuit conditions, the dissociation probability of bound pairs is found to increase from 48% to 70%.