The effect of the growth temperature and V/III flux ratio on the morphology and microstructure of GaAs nanowires grown on GaAs (111) B substrates by Au-assisted molecular beam epitaxy with solid As 4 source was investigated. It has been found that a low growth temperature of 400°C can result in defect-free wurtzite structured nanowire with syringe-like morphology, while nanowires with more homogeneous diameter can be obtained at high temperatures (500°C and 550°C) with many stacking faults. It was also found that, at a low V/III flux ratio, GaAs nanowires had a shrinking neck section, while a high V/III flux ratio may result in disappearance of the shrinking necking section. For the Ga very rich condition, a phase separation of the catalysts can be observed, leaving a small Au–Ga droplet covered by the outer pure Ga droplet.