The new Sb(0)/PANI nanocomposite was successfully synthesized by a one-pot solution phase method. Sb(0) particles were first prepared by the reduction of SbCl5 or SbCl3 using t-BuONa-activated NaH in THF. A ligand exchange with aniline on t-BuONa-stabilized Sb(0) particles yielded aniline-stabilized particles. The Sb(0)/PANI nanocomposite was finally obtained by polymerizing aniline-stabilized Sb(0) particles by using ammonium persulfate. The morphology and the structure of the nanocomposite was examined by transmission electron microscopy (TEM), selected-area electron diffraction (SAED), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Results obtained show that the Sb(0) precursor has a great influence on the size and the crystallinity of Sb(0) nanoparticles dispersed in PANI.