This paper describes the interface reactions and diffusion between silver/polypyrrole (Ag/PPy) composite and silicon substrate. This composite material can be used as a novel technique for 3D-LSI (large-scale integration) by the fast infilling of through-silicon vias (TSV). By immersion of the silicon wafer with via holes into the dispersed solution of Ag/PPy composite, the holes are filled with the composite. It is important to develop a layer between the composite and the Si substrate with good diffusion barrier and adhesion characteristics. In this paper, SiOx and two types of SiOxNy barrier layers with various thicknesses were investigated. The interface structure between the Si substrate, the barrier, and the Ag/PPy composite was characterized by transmission electron microscopy. The adhesion and diffusion properties of the layers were established for Ag/PPy composite. Increasing thickness of SiOx proved to permit less Ag to transport into the Si substrate. SiOxNy barrier layers showed very good diffusion barrier characteristics; however, their adhesion depended strongly on their composition. A barrier layer composition with good adhesion and Ag barrier properties has been identified in this paper. These results are useful for filling conductive metal/polymer composites into TSV.