This paper present the synthesis and characterization of pure (WO3) and doped (Co = 2 and 5 wt.%) in a facile microwave irradiation process, followed by the annealing process at 600°C in air for 6 h in order to know the suitability of the material for superconducting applications. The samples were characterized with powder X-ray diffraction; field emission scanning electron microscopy, UV-VIS diffusion reflectance spectroscopy, and photoluminescence spectroscopy along with, the corresponding magnetic behaviors of the products were analyzed through electron spin resonance spectroscopy and vibrational sample magnetometer. X-ray diffraction patterns showed both undoped and doped WO3.H2O crystallized with orthorhombic phase. The annealing effect showed that doped WO3 (Co ≈ 2 wt.%) formed with orthorhombic phase and the remaining products were found to be monoclinic phase (pure and Co ≈ 5 wt.%) indicating the role of dopant in determining the crystalline phase of the end products. The effect of doping on crystalline perfection of the samples was also monitored using power X-ray analysis. FE-SEM micrographs suggested that the dopants are able to influence the growth rate and morphology of the prepared nanopowders. UV-VIS-DRS spectroscopy was employed to determine the optical band gap of these samples and the results revealed the incorporation of dopant (Co ion) in the intermediate energy level in determining the optical band gap. Blue emissions were verified using PL at room temperature for the annealed samples when exited with 390 nm wavelength. The room temperature PL spectra reveal the distortions in WO42- tetrahedron structure due to microwave irradiation on the samples. The hysteresis loops curve through vibrational sample magnetometer for annealed samples suggest that the cobalt doped samples revealed the suitability of the samples for super conducting applications, In addition with the above the coexistence of dia and ferromagnetism also observed in cobalt doped samples suggests the role of dopant in fixing the magnetic behaviour of the resultant samples.