In organic thin-film transistors (OTFTs), the conducting channel is located near the interface between the organic semiconductor and the oxide dielectric; this interface is crucial for transistor performance. Self-assembled monolayers (SAMs) on the interface reduce the negative influences of the oxide dielectric surface by decreasing the coupling of the carriers at the gate and the role of the active surface defects on transfer. In this paper, we show that SAMs carrying a dipole moment determine the OTFT performance by controlling the charge transfer between the oxide dielectric and the semiconductor. The charges introduced into the semiconductor by this transfer (i.e., residual carriers) lead to a threshold shift to positive values, as well as a decrease in the contact resistance and an increase in the apparent mobility. In this study, other effects of the SAMs, such as the gate potential shift in the channel or a direct reaction between semiconductor and SAM molecules, can be excluded as dominant processes.