We use solvent additives as a simple method to tune the photovoltaic performance of poly-3-hexylthiophene (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) bulk heterojuncton solar cells. 1,2-dichlorobenzene (oDCB) was used as the reference solvent; chlorobenzene (CB) and 1,2,3,4- tetrahydronaphthalene (THN) were used as additives to influence film formation. An increase in the short circuit current and the power conversion efficiency of solar cells with blends cast from mixed solvents was observed. Blends prepared with THN, the highest boiling point solvent, resulted in the best device performance, while blends prepared with the pure reference solvent resulted in the lowest photocurrent. In-plane investigations of the morphology using transmission electron microscopy (TEM) revealed improved phase segregation for blends prepared with mixed solvents, and increased crystallinity in the P3HT phase is demonstrated using atomic force microscopy (AFM) coupled with Kelvin probe force microscopy (KPFM). Optical modeling reveals that the increase in the photocurrent is not due to changes in the optical properties of the blends. Electrical characterization reveals that the electron mobilities decrease slightly in blends cast from mixed solvents, corresponding to a decrease in the fill factor and an increase in P3HT crystallinity observed at the surface of the blend. The increase in the photovoltaic performance is discussed in terms of increased charge separation at the donoracceptor interface due to increased ordering in the P3HT phase induced by the solvent additives.