The quality of the dielectric/organic semiconductor interface is a critical issue, because it determines the charge transport properties in organic thin-film transistors (OTFTs). High-k organic-inorganic hybrid films have received considerable attention for their outstanding dielectric properties, including low leakage currents, high breakdown fields, and suitable band offsets against the organic semiconductor. However, Hf and Zr hybrid gate dielectrics on p-type OTFTs show poor charge transport properties in the organic semiconductor channel, due to the polaron disorder elicited by the high-k properties and the presence of the –N(CH3)2 polarity (hole trapper) on the dielectric/semiconductor interface. In this report, the surface of the Hf and Zr hybrid dielectrics was capped by an ultra-thin poly-1,3,5-trivinyl-1,3,5,-trimethyl-cyclosiloxane (pV3D3) layer formed via an initiated chemical vapor deposition (iCVD) process, to modify the hybrid dielectrics/semiconductor interface. The pV3D3-capped Hf and Zr hybrid OTFTs show an enhanced VT stability while a large amount of VT shift was observed from the Hf and Zr hybrid OTFTs. This large amount of VT shift is attributed to the hole trap sites originated by –N(CH3)2 on the uncapped hybrid dielectrics. Furthermore, the p-type OTFTs with the pV3D3-capped hybrid dielectrics show a higher mobility than those with the uncapped hybrid dielectrics. The presence of the non-polar/low-k pV3D3 on the hybrids contribute to narrow the density of state (DOS) in the organic channel, improving the charge transport properties. This combined approach using the bulk layer of Hf and Zr hybrid films and the pV3D3 capping layer can overcome the limitations of single-layer hybrid dielectrics and improve the overall device performance of the OTFTs.