Polyaniline–silver nanocomposites were synthesized in the form of colloidal particles by the facile one-step aqueous chemical oxidative dispersion polymerization of aniline using silver nitrate as an oxidant and poly(vinyl alcohol) as a colloidal stabilizer. Aniline monomer was oxidized by silver ions, yielding polyaniline and elemental Ag simultaneously. The synthesized nanocomposite particles were colloidally stable over 2 years and transmission electron microscopy studies indicated the production of spherical, plate and rod-shaped polyaniline–silver nanocomposite particles with a silver core–polyaniline shell morphology. The conductivity of a pressed pellet of the nanocomposite particles using the conventional four-point probe technique was 1.4×10 −2 S/cm at 25°C. The nanocomposite particles behaved as a ‘colored’ particulate emulsifier for the stabilization of transparent oil-in-water emulsions.