Recently, we have succeeded in fabricating unconventional bulk glasses by containerless processing. The glasses were colorless and transparent, and high refractive index over 2 in the visible region. We found that the oxygen ions in the glass exhibited a large electronic polarization and existed in a densely packed state. It should be investigated the local structure around W atoms and the connectivity of WOn polyhedra in the glass. However, there are few reports about the structure of WO3-based binary glasses and the glass-forming mechanism of the system is still not clear. In this study, neutron diffraction measurement of WO3-based glasses will be performed. We will combine the data of high energy XRD at SPring-8 and theoretical calculations with the neutron diffraction data, in order to obtain the 3-dimensional atomic configuration of glasses.