We report for the first time the synthesis of well-defined bismuth/phosphorus nanoparticles (Bi/P NPs) based on silyl-halide elimination, by reaction of BiX 3 (X= I, Cl) and P(SiMe 3 ) 3 in the presence of different types of stabilizing ligands, such as cinchonidine, 4-(3phenylpropyl)pyridine and polyvinylpyrrolidone. This synthetic approach led to spherical, small and monodisperse nanoparticles (mean diameter ca. 2.0-2.5 nm determined by TEM). Wideranging characterization of these nanoparticles including TEM, PXRD and SAXS, and several spectroscopic techniques, like X-ray fluorescence, IR and solid state NMR, proved the formation of a core-shell structure constituted by a crystalline Bi(0) core and amorphous P-containing shells, representing a unique case of phase segregation for metal/phosphorus materials reported in the literature. The assessed reactivity of the as-prepared Bi/P NPs evidenced their potential application in the synthesis of phosphine PH 3 in a safer way than the conventional approach using P 4 (white phosphorus) and in a sharp contrast with the reported reactivity of amorphous red phosphorus.