Dielectric surface modifications (DSMs) can improve the performance of organic thin-film transistors (OTFTs) significantly. In order to gain a deeper understanding of this performance enhancement and to facilitate high-mobility transistors, perylene based devices utilizing novel dielectric surface modifications have been produced. Novel DSMs, based on derivates of tridecyltrichlorosilane (TTS) with different functional end-groups as well as polymeric dielectrics have been applied to tailor the adhesion energy of perylene. The resulting samples were characterized by electronic transport measurements, scanning probe microscopy, and X-ray diffraction (XRD). Measurements of the surface free energy of the modified dielectric enabled the calculation of the adhesion energy of perylene upon these novel DSMs by the equation-of-state approach. These calculations demonstrate the successful tailoring of the adhesion energy. With these novel DSMs, perylene thin-films with a superior film quality were produced, which enabled high-performance perylene-based OTFTs with high charge-carrier mobility.