Low-bandgap diketopyrrolopyrrole-based polymer bulk-heterojunction solar cells prepared from different solvents are studied by means of capacitance measurements. Large variations of both photovoltage and photocurrent are induced during device processing by using different solvents that allow internal operating energetics to be addressed. Addition of o-dichlorobenzene to chloroform produces an upward offset of the polymer highest occupied molecular orbital level in accordance with the red shift of the absorption spectra, which correlates with the flat-band potential offset extracted from Mott–Schottky analysis of the reverse and low-forward capacitance. However, the open-circuit voltage does not reach the expected value in the case of chloroform-processed devices because of the reduced occupancy of the acceptor fullerene lower unoccupied molecular orbital states extracted from the chemical capacitance analysis under illumination. This photovoltage loss is linked with the limitation to the increase in the electron Fermi level caused by the reduced charge density involved in the photovoltaic process, as derived from the morphology-influenced short-circuit current density.