Semiconductor nanowires of III–V materials have generated much interest in recent years. However, the growth mechanisms by which these structures form are not well understood. The so‐called vapor–liquid–solid (VLS) mechanism has often been proposed for III–V systems, with a chemically inert, liquid metal particle (typically Au) acting as a physical catalyst. We assert here that Au is, in fact, not inert with respect to the semiconductor material but rather interacts with it to form a variety of intermetallic compounds. Moreover, we suggest that III–V nanowire growth can best be understood if the metallic particle is not a liquid, but a solid‐phase solution or compound containing Au and the group III material. The four materials GaP, GaAs, InP, and InAs will be considered, and growth behavior related to their particular temperature‐dependent interaction with Au.