Microscopic Understanding of the Growth and Structural Evolution of Narrow Bandgap III–V Nanostructures

III–V group nanomaterials with a narrow bandgap have been demonstrated to be promising building blocks in future electronic and optoelectronic devices. Thus, revealing the underlying structural evolutions under various external stimuli is quite necessary. To present a clear view about the structure–property relationship of III–V nanowires (NWs), this review mainly focuses on key procedures involved in the synthesis, fabrication, and application of III–V materials-based devices. We summarized the influence of synthesis methods on the nanostructures (NWs, nanodots and nanosheets) and presented the role of catalyst/droplet on their synthesis process through in situ techniques. To provide valuable guidance for device design, we further summarize the influence of structural parameters (phase, defects and orientation) on their electrical, optical, mechanical and electromechanical properties. Moreover, the dissolution and contact formation processes under heat, electric field and ionic water environments are further demonstrated at the atomic level for the evaluation of structural stability of III–V NWs. Finally, the promising applications of III–V materials in the energy-storage field are introduced.