A one-step process for the production of all-organic, all-solution-processed field-effect transistors (FETs) can be achieved using triethylsilylethynyl anthradithiophene (TES-ADT). TES-ADT has a lower surface energy than poly(methyl methacrylate) (PMMA), which results in a segregation and crystal formation of TES-ADT at the air-film interface after spin-casting and subsequent solvent annealing. The resulting FETs comprise vertically phase-separated semiconducting and dielectric layers and exhibit high performances.