To obtain safe, high-performance Li-ion batteries, the development of electrolytes with high impact resistance and high ionic conductivity is important. Ionic conductivity at room temperature has been improved by using poly(ethylene glycol) (PEG) diacrylate (PEGDA) to form three-dimensional (3D) networks and solvated ionic liquids. However, the effects of the molecular weight of PEGDA on ionic conductivities and the relationship between ionic conductivities and network structures of cross-linked polymer electrolytes have not been discussed in detail. In this study, the dependence of the ionic conductivity of photo-cross-linked PEG solid electrolytes on the molecular weight of the PEGDA was evaluated. X-ray scattering (XRS) gave detailed information about the dimensions of 3D networks formed by the photo-cross-linking of PEGDA, and the effects of the network structures on the ionic conductivities were discussed.