We discuss an alternative route to determine the solubility parameters of two prototype organic semiconductors, namely the semi-crystalline polymer poly-(3-hexylthiophene-2,5-diyl) (P3HT) and the methano-fullerene derivative [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM). The HSP (Hansen solubility Parameters) derived by this novel method are compared to the findings derived from the classical multi-solvent method to determine the HSP, and significantly higher accuracy is found. For this novel approach we designed two component solvent blend systems, being composed by mixing a solvent with a non-solvent. Varying the composition of the solvent - non-solvent blends from 0% to 100% gradually converts a solvent into a non-solvent. This very accurate control of the dispersive, polar and hydrogen contributions to the overall solubility now allows determining the Hansen sphere for P3HT and PCBM with much higher accuracy. The transition from a solvent into a non-solvent was further followed by solar cell investigations. Comparing the solubility studies with device investigations allows identifying the processing limits of solvent systems. (C) 2012 Elsevier B.V. All rights reserved.