The P4VP electrografting process realized on chemically oxidized p-type silicon surface, instead of traditional oxide free surface, leads to a thicker grafted polymer film. In this paper, we studied the influence of the surface states generated during the chemical oxidation of the silicon surface, on the thickness of the P4VP film. We used electrochemical measurements and Mott-Schottky plot analysis to demonstrate that such an oxidized surface does not only allow the electrografting process to occur, but also increases the accumulation of electrons at the silicon interface. In this condition, the chemical oxidation of silicon surface enhances the electro-initiation of the P4VP electrografting process and promotes the polymer growth. Silicon based technologies are widely used in microelectronics. Traditionally, the electrical insulation of silicon surfaces is achieved through the Chemical Vapor Deposition (CVD) or the thermal growth of a silicon dioxide layer. Nevertheless, silicon insulation in highly non-planar microstructures like MEMS and vertical interconnects remains a challenge. For example, in 3D Integrated Circuit (3D IC) planar dies are stacked and connected to each other using vertical interconnections most often named Through Silicon Via (TSV).1,2 The insulation of high aspect ratio copper TSV using SiO 2 is problematic. Indeed, the insulation of the TSV must be realized at temperature below 400• C (to preserve the integrity of the underlying CMOS). The use of thermally grown silicon oxide is not possible as it requires a higher process temperature (typically over 600• C). CVD based SiO 2 processes are therefore utilized. Nevertheless, the deposition of a good conformal SiO 2 film to insulate high aspect ratio TSV is hardly achievable and is costly due to the required growth condition of CVD methods. 1,3 During the last decade, Si insulation using polymer films was developed as an alternative to traditional SiO 2 . Among them, the chemical vapor deposition of parylene (poly(p-xylylene)) films 3-6 and the electrografting of poly-4-vinylpyridine (P4VP) in aqueous media have shown promising results.7-9 Indeed, they can be deposited at room temperature or up to 300• C. 3,10 Parylene HT films have been demonstrated to be stable up to a temperature of 350• C 11 , to avoid the appearance of cracks and adhesion loss in the dielectric film. 5,12 Electrografted P4VP were shown to withstand temperatures up to 450• C, 8 making this process a more versatile alternative to SiO 2 and parylene for silicon insulation in microelectronic systems.The electrografted P4VP films present similar dielectric properties as those of SiO 2 films.8 They are highly conformal with strong adhesion properties (covalent bonds) with the Si surface. 7,10 It is also compatible with NiB electroless processes that can be used as a copper diffusion barrier layer.8 So far, the compatibility of the P4VP electrografting process has been reported on high aspect ratio copper TSV, such as used for silicon interposers 7,8 and in Via-Last integratio...