Recently, great interest has been devoted to cost-effective alternative energy sources such as organic solar cells because of the mechanical flexibility and the versatility of chemical structure, the low cost of fabrication, and ease of processing. As regards this last point, the possibility to deposit organic materials from solutions at low temperatures makes them employable for fabricating printed solar cells by direct printing methods. In this study, we used the inkjet-printing technology to deposit P3HT blends with various fullerene acceptors (PCBM, PCBM and bisPCBM) dissolved in single solvents, 1,2-dichlorobenzene (DCB) and chlorobenzene (CB), and their mixtures. After optimizing the printing parameters (printhead speed, drop emission frequency, and substrate temperature), the effect of the solvents on the morphology of the photoactive layers was analyzed through Raman spectroscopy and atomic force microscopy. Polymer solar cells with the structure glass/ITO/PEDOT:PSS/blend/Ca/Al were fabricated and characterized by current-voltage (I-V) measurements under 100 mW/cm2 AM 1.5G illumination. A comparative study of the performances of the devices was performed based on three different fullerene derivatives, correlating them to the microstructure of the printed blend films. The optimal devices were obtained when the blend films were deposited from a mixture of DCB:CB 4:1 by volume: this was in agreement with the most favorable morphology of these films. © 2012 Springer Science+Business Media.