AbstractGaAs nanowire (NW) growth was studied by metal‐organic vapour phase epitaxy (MOVPE). The vapour–liquid–solid (VLS) mechanism with gold‐based alloy particles and the selective‐area growth (SAG) mechanism on electron beam lithographically prepared SiNx/GaAs mask structures were applied. A special focus is set on thermodynamic aspects of the VLS process. The alloy particle formation and the influence of MOVPE growth parameters on the growth rate and the GaAs NW morphology are examined. Furthermore, the improvement of the real structure with particular interest on the twin formation is studied. Besides the commonly used continuous VLS growth mode also a pulsed VLS growth mode with alternating precursor supply is reported. Based on photoluminescence measurements the effect of strain in core/shell NW structures is confirmed. For the SAG mechanism the MOVPE growth parameters are determined and the real structure is described. magnified image