Herein, we demonstrate the ability of Zn to catalyze the growth of Si nanowires via reaction temperature determined, vapour-liquid-solid (VLS) or vapour-solid-solid (VSS) growth mechanisms. This is the first reported use of a type B catalyst to grow Si nanowires via the VSS mechanism to our knowledge whereby the highly faceted Zn seeds resulted in an increased NW diameter. This was used to induce diameter variations along the axial length of individual nanowires by transitioning between VLS and VSS growth.