Previous studies have examined the bundled structure of W18O49 nanowhiskers with diameters exceeding 80 nm, noting that the space between individual domains was amorphous. However, in contrast to these findings , every region of the nanowhisker cross-section presented in this study (as seen in Fig. and) was distinctly crystalline and consistently oriented along the [010] axis. This cross-section (Fig. ) predominantly features the W18O49 structure, interwoven with other domains constituted of related W-O phases, specifically the structural motifs of fully oxidized WO3 (Fig. ), W20O58 (Fig. ), and W12O34 (Fig. ). The W18O49 lattice (Fig. ) embodies two quintessential structural motifs: hexagonal channels formed by six [WO6] octahedra and pentagonal columns assembled from a central pentagonal bipyramidal polyhedron [WO7], encircled by five [WO6] octahedra. These motifs in Fig. are highlighted with a blue hexagon and a yellow pentagon, respectively. The emergence of the hexagonal channel can be perceived as a compensation for the lattice distortion. This rearrangement stems from the formation of pentagonal column through the removal of oxygen from the WO3 lattice. This structural rearrangement produces a relatively stable phase compared to other Mágneli tungsten suboxide phases. Importantly, two edge-linked pentagonal columns found in the W18O49 are the structural element motif containing the tungsten in the oxidation state 5+. Contra intuitively, the W 5+ are not the ones in the pentagonal bipyramidal coordination but the central atoms in octahedra sharing edges. These W 5+ -W 5+ pairs are responsible for unique absorption properties in the near infrared regions and other electronic features, like bipolarons. Next to the W18O49 phase, a significant portion of the analyzed section is composed of a fully oxidized array of [WO6] octahedra, forming a WO3 lattice (Fig. ). Between these WO3 regions, other structural motifs are observed, notably a lattice resembling the W20O58 phase (Fig. ). In analogy to the W20O58 lattice, which consists of a repeating unit of three closely packed pairs of [WO6] octahedra and a distorted hexagonal channel, the observed motif features an extended pair line by an additional octahedral pair (indicated by a yellow stretched irregular hexagon). The shear plane stacking is counterbalanced by pairs of distorted hexagons (marked in blue), which are also characteristic of the W20O58 phase. Such W20O58 resembling structural motif is present in various places over the analyzed cross-section differing by size and orientation. Intriguingly, another arrangement of pentagonal columns was identified (Fig. ),