Since tungsten trioxide has a desirable band gap of 2.6–2.8 eV, which boosts its ability to absorb radiation in the visible range, which become the most researched transition metals of the modern era. It is a polymorphic n-type semiconductor that may take on various different shapes, including triclinic, monoclinic, hexagonal, orthorhombic, and tetragonal. Some of its uses include, among others, solar cells, gas sensors, electrochromic devices, and photocatalytic reactions. WO3 might usually be employed in the form of powder or immobilized. Numerous techniques are proposed by researchers for the synthesis of WO3, with the most popular ones being thermal evaporation, sol–gel, chemical vapor deposition, electrospinning, sputtering, and electron beam. An efficient and adaptable technique for creating nano- and ultrafine-fibers is electrospinning. Significant advancements have been achieved in the technology used to create these samples, such as the engineering of electrospun nanofibers to fulfill or permit their implementation in the widest range of applications. In this regard, our study aims to present a thorough understanding of the application of the electrospinning technology to the creation of WO3 nanostructures, which will be used as semiconductors in experiments involving heterogeneous photocatalysis.