Self-assembled monolayers are widely used to modify the gate dielectric/semiconductor interface in organic thin-film transistors. By modifying the interaction between the molecular semiconductor and the substrate, thin-film ordering and the electronic properties of the semiconducting channel can be controlled. The modified semiconductor/dielectric properties result in macroscopically observed changes in the charge-carrier mobilities, threshold voltages, subthreshold swing and transfer characteristic hysteresis. The latter two are determined by the density of charge-trapping states at the interface. Here, we investigate the influence of the thickness of the self-assembled monolayer, via the alkyl chain length in n-alkyl phosphonic acid-based monolayers on SiO 2 , on the electronic properties of pentacene-based organic thin-film transistors. Rather than a monotonic increase or decrease in performance with increasing chain length, we have found that the optimum performance occurs with chains of 8–10 carbon atoms. Atomic force microscopy shows a correlation between pentacene crystalline grain size and transistor performance.