We have investigated self-assembled monolayer (SAM) treatment on SiO 2 gate insulator of poly(3-hexylthiophene) (P3HT) thin-film transistor (TFT), and demonstrated a correlation between mobility and surface free energy of the insulator. The device with lower surface free energy shows higher mobility. The docosyltrichlorosilane (DCTS)-treated device exhibits the best performance among the various SAM-treated devices examined. Field-effect mobility, on/off ratio and threshold voltage of the DCTS-treated P3HT TFT were 0.015cm 2 /Vs, >10 5 and −14V, respectively.