The aim of the present work focuses the role of “Mg” in WO3.H2O nanopowders, doped with Magnesium using a facile microwave irradiation process and the annealing process was carried out at 600°C in air for 6 h in order to remove the impurities and enhance the crystallinity of the end products. The samples were further characterized by powder X-ray diffraction, field emission scanning electron microscopy, UV-VIS diffusion reflectance spectroscopy, and the relevant magnetic behaviors of the products were carried out using vibrational sample magnetometer to find out the suitability of the material for superconducting applications. Powder X-ray diffraction confirmed that the samples both undoped and doped WO3.H2O crystallized with orthorhombic phase respectively. On the other hand, annealing effect on the samples formed with orthorhombic phase. It clearly shows the doping on crystalline nature of the samples was also monitored using power X-ray analysis. Observations from FE-SEM micrographs suggested that the samples having influence with dopants in growth rate along with morphology of the prepared nanoparticles. UV-VIS-DRS spectroscopy was an important tool used to find the optical band gap of these samples and the results revealed the contribution of the dopant materials in the the optical band gap values using KM model and the corresponding blue shift was observed with 360 nm wavelength. The interesting results from hysteresis loops from vibrational sample magnetometer on the annealed samples showed that the doped samples try to explore well into the superconducting or diamagnetic state reveal the suitability of the prepared materials for superconducting applications.