In this study, a spin-coating method is demonstrated for producing silver nanowire films on flexible polyethylene terephthalate substrates. To improve the inherent, poor uniformity in conductivity and lower the high surface roughness of silver nanowire films, a composite film based on a silver nanowire network and polyvinyl alcohol was fabricated by a mechanical lamination technique. The effects of mechanical pressure and lamination time on the photoelectric characterization of the composite films were investigated. Stable electrical channels of a silver nanowire network were established on the substrate by laminating the composite layers using a pressure of 30 MPa for 10 min. A transmittance of 86.9% at a wavelength of 550 nm with a sheet resistance of 0.75 Ω sq⁻¹ and a haze of 7.1% were measured for the silver nanowire–polyvinyl alcohol film. Furthermore, the composite film also showed low surface roughness, stable conductivity after 300 bending cycles, as well as the improved weak adhesion of nanowires to the substrate due to the compact contact between silver nanowires and polyvinyl alcohol.