Silver-doped polyaniline–polyvinyl chloride (PVC) nanocomposite films (Ag.PANI–PVC) were synthesized by non-solvent-induced phase inversion method. The nanomaterials were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, ultraviolet, and field emission scanning electron microscopy analysis. Thermal stability and tensile strength of the Ag-doped and undoped PANI–PVC films were studied. The photocatalytic activity of the nanocomposites on methylene blue dye under visible light was evaluated at different initial concentrations of the dye. Silver-doped nanocomposites exhibited excellent photodegradation efficiency. The kinetics of photocatalysis fit well to the pseudo first-order model. Antibacterial performance of the samples was tested against Staphylococcus aureus and Escherichia coli bacteria by agar disc diffusion method. It was observed that Ag.PANI–PVC and Ag.PANI have antagonistic effects against the growth of gram-positive bacteria (S. aureus) and gram-negative bacteria (E. coli) with inhibition zones in the range of 10–35 mm.