Nanostructural gold/polyaniline core/shell composite particles on conducting electrode ITO were successfully prepared via electrochemical polymerization of aniline based on 4-aminothiophenol (4-ATP) capped Au nanoparticles. The new approach to the fabrication included three steps: preparation of gold nanoparticles as core by pulse electrodeposition; formation of ATP monolayer on the gold particle surface, which served as a binder and an initiator; polymerization of aniline monomer initiated by ATP molecules under controlled voltage lower than the voltammetric threshold of aniline polymerization, which assured the formation of polyaniline shell film occurred on gold particles selectively. Topographic images were also studied by AFM, which indicated the diameter of gold nanoparticles were around 250 nm. Coulometry characterization confirmed the shell thickness of polyaniline film was about 30 nm.A possible formation mechanism of the Au/polyaniline core-shell nanocomposites was also proposed. The novel as-prepared core-shell nanoparticles have potential application in constructing biosensor when bioactive enzymes are absorbed or embedded in polyaniline shell film.