In this report, we investigate the impact of the molecular dipole moment and redox active head groups (C60) in pure and mixed self-assembled monolayers (SAMs), which serve as an ultra-thin hybrid dielectric layer in low-voltage operating organic thin-film transistors. We show that the dipole of the SAM-forming molecules affects the threshold voltage, while the concentration of redox-active C60 moieties determines the hysteresis in devices with α,α′-dihexyl-sexithiophene and pentacene as organic semiconductors.