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Hierarchical structures of self-assembled three-dimensional (3D) WO 3 eAg were synthesized via hydrothermal growth using precursor solutions of peroxopolytungstic acid with different amounts of Ag. The as-grown samples were analyzed by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, ultravioletevisible spectroscopy, and X-ray photoelectron spectroscopy. The XRD and Raman studies showed that as the amount of Ag was varied from 0 to 10 wt% in the hydrothermal growth solution, the crystal phase gradually changed from orthorhombic WO 3 $0.33H 2 O to hexagonal WO 3. The FTIR and TGA studies revealed different hydration levels, supporting the XRD and Raman results. By controlling the amount of Ag in the precursor solution, platelet-like building blocks and hexagonal building blocks were obtained, highlighting the role of Ag in the hydrothermal growth of 3D WO 3 $0.33H 2 O and WO 3 microcrystals. In addition, high-magnification FESEM images showed that the Ag nanoparticles were anchored on the surface of the 3D hierarchical WO 3 eAg structures, and the UVevis measurements demonstrated that the 3D hierarchical structures gradually absorbed more light when the Ag content was increased. Moreover, the band-gap energy decreased when the Ag content was increased from 0 wt% (E g ¼ 2.65 eV) to 10 wt% (E g ¼ 2.26 eV). These experimental results demonstrate that the amount of Ag played a crucial role in determining the building blocks' morphology, and the hydration level, optical properties, and crystal phase of the WO 3 $nH 2 O microcrystals.

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