A single step metal assisted etching (MAE) process, utilizing metal ion-containing HF solutions in the absence of an external oxidant, has been developed to generate heterostructured Si nanowires with controllable porous (isotropically etched) and non-porous (anisotropically etched) segments. Detailed characterisation of both the porous and non-porous sections of the Si nanowires was provided by transmission electron microscopy studies, enabling the mechanism of nanowire roughening to be ascertained. The versatility of the MAE method for producing heterostructured Si nanowires with varied and controllable textures is discussed in detail.