Free standing polypyrrole-silver nanocomposite films were prepared by interfacial photopolymerization of pyrrole (in DCM) using AgNO₃ (aqueous) as photosensitizer. During the photopolymerization process, film formation starts first at the DCM–water interface and later at the air–water interface. The films prepared at the air–water interface are thin (<1 μm), flexible, having a very low content of uniformly distributed metallic Ag nanoparticles and exhibiting high electrical conductivity ∼14.8 S cm⁻¹. The thick films (∼200 μm) prepared at the DCM–water interface are porous, mechanically weak, contain a very high amount of Ag micro and nanoparticles and exhibit two orders of magnitude lower conductivity ∼0.1 S cm⁻¹. High conductivity of PPy-Ag films formed at the air–water interface is attributed to controlled polymerization due to the limited availability of pyrrole and Ag⁺ ions at this interface.