The formation and processing of organic insulators on the device performance have been studied in the fabrication of organic thin film transistors (OTFTs). The series of polyvinyls, poly-4-vinyl phenol(PVP) and polyvinyltoluene (PVT), were used as solutes and propylene glycol monomethyl ether acetate(PGMEA) as a solvent in the formation of organic insulators. The cross-linking of organic insulators was also attempted by adding the thermosetting material, poly (melamine-co-formaldehyde) as a hardener in the compound. The electrical characteristics measured in the metal-insulator-metal (MIM) structures showed that insulating properties of PVP layers were generally superior to those of PVT layers. Among the layers of PVP series: PVP(10 wt%) copolymer, 5 wt% cross-linked PVP(10 wt%), PVP(20 wt%) copolymer, 5 wt% cross-linked PVP(20 wt%) and 10 wt% cross-linked PVP(20 wt%), the 10 wt% cross-linked PVP(20 wt%) layer showed the lowest leakage current characteristics. Finally, inverted staggered OTFTs using the PVP(20 wt%) copolymer, 5 wt% cross-linked PVP(20 wt%) and 10 wt% cross-linked PVP(20 wt%) as gate insulators were fabricated on the polyether sulphone (PES) substrates. In our experiments, we could obtain the maximum field effect mobility of 0.31 in the device from 5 wt% cross-linked PVP(20 wt%) and the highest on/off current ratio of in the device from 10 wt% cross-linked PVP(20 wt%).