Abstract: Ag nanoparticles were sputter-deposited on ammonium persulfate ((NH₄)₂S₂O₈) powder to obtain (NH₄)₂S₂O₈-Ag powder, which was used to synthesize the HCl-doped polyaniline-Ag (HCl-PANI-Ag) composite via a polymerization procedure. The Ag nanoparticles were dispersed in the HCl-PANI matrix, and their sizes mainly ranged from 3 to 6 nm. The Ag nanoparticles did not affect the structure of emeraldine salt in the composite, and they increased the ordered crystalline regions in the HCl-PANI matrix. The HCl-PANI-Ag composite had a conductivity of (6.8 ±0.1) S/cm, which is about four times larger than that of the HCl-PANI. The charge transport mechanism in the composite is explained by the three-dimensional Mott variable-range hopping (3D-Mott-VRH).