Tungsten suboxide W ₁₈O ₄₉ nanowhiskers are a material of great interest due to their potential high-end applications in electronics, near-infrared light shielding, catalysis, and gas sensing. The present study introduces three main approaches for the fundamental understanding of W ₁₈O ₄₉ nanowhisker growth and structure. First, W ₁₈O ₄₉ nanowhiskers were grown from γ-WO ₃/a-SiO ₂ nanofibers in situ in a scanning electron microscope (SEM) utilizing a specially designed microreactor (μReactor). It was found that irradiation by the electron beam slows the growth kinetics of the W ₁₈O ₄₉ nanowhisker, markedly. Following this, an in situ TEM study led to some new fundamental understanding of the growth mode of the crystal shear planes in the W ₁₈O ₄₉ nanowhisker and the formation of a domain (bundle) structure. High-resolution scanning transmission electron microscopy analysis of a cross-sectioned W ₁₈O ₄₉ nanowhisker revealed the well-documented pentagonal Magnéli columns and hexagonal channel characteristics for this phase. Furthermore, a highly crystalline and oriented domain structure and previously unreported mixed structural arrangement of tungsten oxide polyhedrons were analyzed. The tungsten oxide phases found in the cross section of the W ₁₈O ₄₉ nanowhisker were analyzed by nanodiffraction and electron energy loss spectroscopy (EELS), which were discussed and compared in light of theoretical calculations based on the density functional theory method. Finally, the knowledge gained from the in situ SEM and TEM experiments was valorized in developing a multigram synthesis of W ₁₈O ₄₉/a-SiO ₂ urchin-like nanofibers in a flow reactor.