The paradodecatungstate anions covered in this review span a continuum from molecular clusters to morphology-controlled tungsten trioxide (WO₃) nanomaterials. The synthesized cluster compounds by using paradodecatungstate anions with various metal ions have various applications as precursors for the fabrication of tungsten carbide (WC), tungsten nitride (WN_x) and tungsten trioxide (WO₃) nanomaterials. The relationship between the synthetic approaches for the synthesis of morphology-controlled WO₃ and their potential applications (such as photocatalytic activity, photodegradation, oxidation process, sensing and adsorption) has enhanced research interest in thoroughlyanalyzing these nanomaterials. Furthermore, some of the main synthetic approaches to synthesize WO₃ and their hydrates (for improving the surface area, pore size and volume) are systematically summarized and highlighted. It is projected that this review article could propose strategies for designing hierarchical WO₃-based nanomaterials with low expenditure and high competence, which could possess a promising scenario of applications to meet the urgent demand of nanomaterials with variable morphologies, such as nanorods, nanotubes, nanowires, nanofibres, nanosheets, nanoplates, nanoflowers and nanoflakes. The objectives of this review are to thoroughly study the various aspects for the synthesis and design of novel WO₃ with low cost and high efficiency, the role of the paradodecatungstate anion-based clusters as precursors in their synthesis, and to apply these nanomaterials for various potential applications. Recent progress in the nano-sized WO₃ and their hydrates has made their prospective applications even more attractive to researchers, bringing in colossal research challenges and even terrific opportunities for more constructive applications.