Abstract Bi-containing III-V semiconductors constitute an exciting class of metastable compounds with wide-ranging potential optoelectronic and electronic applications. However, the growth of III-V-Bi alloys requires group-III-rich growth conditions, which pose severe challenges for planar growth. In this work, we exploit the naturally-Ga-rich environment present inside the metallic droplet of a self-catalyzed GaAs nanowire (NW) to synthesize metastable GaAs/GaAs_1−x Bi _x axial NW heterostructures with high Bi contents. The axial GaAs_1−x Bi _x segments are realized with molecular beam epitaxy by first enriching only the vapor–liquid–solid (VLS) Ga droplets with Bi, followed by exposing the resulting Ga-Bi droplets to As₂ at temperatures ranging from 270 °C to 380 °C to precipitate GaAs_1−x Bi _x only under the NW droplets. Microstructural and elemental characterization reveals the presence of single crystal zincblende GaAs_1−x Bi _x axial NW segments with Bi contents up to (10 ± 2)%. This work illustrates how the unique local growth environment present during the VLS NW growth can be exploited to synthesize heterostructures with metastable compounds.