The phase-separation characteristics of spin-cast difluorinated-triethylsilylethynyl anthradithiophene (F-TESADT)/poly(methyl methacrylate) (PMMA) blends are investigated with the aim of fabricating transistors with a high field-effect mobility and stability. It is found that the presence of PMMA in the F-TESADT/PMMA blends prevents dewetting of F-TESADT from the substrate and provides a platform for F-TESADT molecules to segregate and crystallize at the air–film interface. By controlling the solvent evaporation rate of the spin-cast blend solution, it is possible to regulate the phase separation of the two components, which in turn determines the structural development of the F-TESADT crystals on PMMA. At a low solvent evaporation rate, a bilayer structure consisting of highly ordered F-TESAT crystals on the top and low-trap PMMA dielectric on the bottom can be fabricated by a one-step spin-casting process. The use of F-TESADT/PMMA blend films in bottom gate transistors produces much higher field-effect mobilities and greater stability than homo F-TESADT films because the phase-separated interface provides an efficient pathway for charge transport.