Résumé : Thin films of bi-component mixtures of two commonly used n- and p-type organic semiconductors are found to undergo spontaneous phase-separation with the formation of well-ordered nanoneedles/crystals upon solvent-vapour annealing. The de-mixing is used to fabricate ambipolar organic field-effect transistors where balanced mobilities were achieved by adjusting the relative amount of the constituent in solution. © 2012 The Royal Society of Chemistry.