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The authors performed transient photocurrent measurements under applied bias and electroabsorption spectroscopy on devices based on a pristine poly(phenylene vinylene) derivative as well as its mixture with 1% of a methanofullerene electron acceptor. Combining both techniques allows us to directly determine the internal electric field and to conclude on its implication on the photovoltaic performance of the devices. The electric field is identified as the driving force of the photocurrent, hence indicating the maximum obtainable photovoltage. Acceptor concentrations as low as 1% shift the energetic alignment of the top electrode to the reduction potential of the acceptor, reducing the internal electric field.