Polymer dielectric materials with hydroxyl functionalities such as poly(4-vinylphenol) and poly(vinyl alcohol) been utilized widely in organic thin-film transistors (OTFTs) because of their excellent insulating performance gained by hydroxyl-mediated cross-linking. However, the polar hydroxyl functionality also deleteriously affects the performance of OTFTs and significantly impairs the device stability. In this study, a sub-20 nm, high-k copolymer dielectric with hydroxyl functionality, poly(2-hydroxyethyl acrylate-co-di(ethylene glycol) divinyl ether), was synthesized in the vapor phase via initiated chemical vapor deposition. The inherently dry environment offered by the vapor phase polymer synthesis prompted the snuggling of polar hydroxyl functionalities into the bulk polymer film to form a molecular thin hydrophobic skin layer at its surface, verified by near-edge X-ray absorption fine structure analysis. The chemical composition of the copolymer dielectric was optimized systematically to achieve high dielectric constant (k approximate to 6.2) as well as extremely low leakage current densities (less than 3 X 10(-8) A/cm(2) in the range of +/- 2 MV/cm) even with sub-20 nm thickness, leading to one of the highest capacitance (higher than 300 nF/cm(2)) achieved by a single polymer dielectric to date. Exploiting the structural advantage of the cross-linked high-k polymer dielectric, high-performance OTFTs were obtained. Notably, the spontaneously formed molecular thin, hydrophobic skin layer in the copolymer film substantially suppressed the hysteresis in the transistor operation. The trap analysis also suggested the formation of bulk trap with a high energy barrier and sufficiently low trap densities at the semiconductor/dielectric interface, owing to the surface skin layer. Furthermore, the OTFTs with the OH-containing copolymer dielectric showed an unprecedentedly excellent operational stability. No apparent OTFT degradation was observed up to 50 000 s of high constant voltage stress (corresponding to the applied electric field of 1.4 MV/cm) because of the markedly suppressed interfacial trap density by the hydrophobic skin layer, together with the current compensation by the bulk hydroxyl functionalities. We believe that the surface modification-free, one-step polymer dielectric synthetic strategy will provide a new insight into the design of polymer dielectric materials for high-performance, low-power soft electronic devices with high operational stability.