Polymer:fullerene blends were screened in a combinatorial approach using inkjet printing thin film libraries for photovoltaic devices. The application of inkjet printing enabled a fast and simple experimental workflow from film preparation to the study of structure-property-relationships with a very high material efficiency. Inkjet printing requires less material for the preparation of thin film libraries in comparison to other dispensing techniques, like spin-coating. Two polymers (PCPDTBT, PSBTBT) and two fullerene derivatives (mono-PCBM, bis-PCBM) were investigated in various blend ratios, concentrations, solvent ratios, and film thicknesses. Morphological and optical properties of the inkjet printed films were investigated and compared with spin-coated films. This study shows the principle of an experimental setup from solution preparation to film characterization for the combinatorial investigation of large polymer:fullerene libraries.