Scanning transmission electron microscopy (STEM) was successfully applied to the analysis of silicon nanowires (SiNWs) that were self-assembled during an inductively coupled plasma (ICP) process. The ICP-synthesized SiNWs were found to present a Si-SiO2 core-shell structure and length varying from ≈100 nm to 2-3 μm. The shorter SiNWs (maximum length ≈300 nm) were generally found to possess a nanoparticle at their tip. STEM energy dispersive X-ray (EDX) spectroscopy combined with electron tomography performed on these nanostructures revealed that they contain iron, clearly demonstrating that the short ICP-synthesized SiNWs grew via an iron-catalyzed vapor-liquid-solid (VLS) mechanism within the plasma reactor. Both the STEM tomography and STEM-EDX analysis contributed to gain further insight into the self-assembly process. In the long-term, this approach might be used to optimize the synthesis of VLS-grown SiNWs via ICP as a competitive technique to the well-established bottom-up approaches used for the production of thin SiNWs.