A novel application of ethylene-norbornene cyclic olefin copolymers (COC) as gate dielectric layers in organic field-effect transistors (OFETs) that require thermal annealing as a strategy for improving the OFET performance and stability is reported. The thermally-treated N,N′-ditridecyl perylene diimide (PTCDI-C13)-based n-type FETs using a COC/SiO2 gate dielectric show remarkably enhanced atmospheric performance and stability. The COC gate dielectric layer displays a hydrophobic surface (water contact angle = 95° ± 1°) and high thermal stability (glass transition temperature = 181 °C) without producing crosslinking. After thermal annealing, the crystallinity improves and the grain size of PTCDI-C13 domains grown on the COC/SiO2 gate dielectric increases significantly. The resulting n-type FETs exhibit high atmospheric field-effect mobilities, up to 0.90 cm2 V−1 s−1 in the 20 V saturation regime and long-term stability with respect to H2O/O2 degradation, hysteresis, or sweep-stress over 110 days. By integrating the n-type FETs with p-type pentacene-based FETs in a single device, high performance organic complementary inverters that exhibit high gain (exceeding 45 in ambient air) are realized.