This study investigates a spin-coating method for modifying the surface properties of a poly(ethylene-alt-maleic anhydride) (PEMA) gate insulator. The 60 nm-thick PEMA thin film exhibits excellent electrical insulating properties, and its surface properties could be easily modified by surface grafting of octylamine. Due to surface treatment via spin-coating, the surface energy of the PEMA gate insulator decreased, the crystal quality of the organic semiconductor improved, and consequently the performance of low-voltage organic thin-film transistors (TFTs) was enhanced. Our results suggest that the surface treatment of the PEMA gate insulator could be a simple and effective method for enhancing the performance of organic TFTs.