Inorganic materials such as SiOx and SiNx are commonly used as dielectric layers in thin-film transistors (TFTs), but recent advancements in TFT devices, such as inclusion in flexible electronics, require the development of novel types of dielectric layers. In this study, CVD-deposited poly(p-xylylene) (PPx)-based polymers were evaluated as alternative dielectric layers. CVD-deposited PPx can produce thin, conformal, and pinhole-free polymer layers on various surfaces, including oxides and metals, without interfacial defects. Three types of commercial polymers were successfully deposited on various substrates and exhibited stable dielectric properties under frequency and voltage sweeps. Additionally, TFTs with PPx as a dielectric material and an oxide semiconductor exhibited excellent device performance; a mobility as high as 22.72 cm2/(V s), which is the highest value among organic gate dielectric TFTs, to the best of our knowledge. Because of the low-temperature deposition process and its unprecedented mechanical flexibility, TFTs with CVD-deposited PPx were successfully fabricated on a flexible plastic substrate, exhibiting excellent durability over 10000 bending cycles. Finally, a custom-synthesized functionalized PPx was introduced into top-gated TFTs, demonstrating the possibility for expanding this concept to a wide range of chemistries with tunable gate dielectric layers.