Metal-assisted chemical etching (MACE) of silicon (Si) is a simple and low-cost process to fabricate Si nanostructures with varying aspect ratio and properties. In this work, we report on the structural and vibrational properties of Si nanostructures synthesized with varying metal catalyst. The morphology of the synthesized nanowires was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The optical and vibrational properties of the Si nanostructures were studied by photoluminescence and Raman spectroscopy using three different excitation sources (UV, visible and near-infrared) and are correlated to their microstructures. We propose that the excessive injection of holes into Si at the metal-Si interface and its diffusion to the nanowire surfaces facilitate the etching of Si on these surfaces, leading to a mesoporous network of Si nanocrystallites. When etched with catalytic Au nanoparticles, “hay-stacked” mesoporous Si nanowires were obtained. The straighter nanowires etched with Ag nanoparticles, consisted of a single crystalline core with a thin porous layer that decreased in thickness towards the base of the nanowire. This difference is due to the higher catalytic activity of Au compared to Ag for H2O2 decomposition. The SERRS observed during UV and visible Raman with Ag-etched Si nanowires and near-infrared Raman with Au-etched Si nanowires is due to the presence of the sunken metal nanoparticles. In addition, we explored the influence of varying H2O2 and HF concentration as well as the influence of increased etching temperature on the resultant nanostructured Si morphology. Such Si nanostructures may be useful for a wide range of applications such as photovoltaic and biological and chemical sensing.