The green synthesis of nanoparticles has become a matter of great interest in recent times and proposed as an environmentally friendly alternative to chemical and physical methods. Blend of polyethylene oxide (PEO)/starch (70/30 wt%) doped with various concentrations of gold nanoparticles (Au NPs) were prepared by casting technique. X-ray diffraction (XRD) shows the semi-crystalline nature of all prepared samples. It also shows an increase in the amorphous region due to raising the doping level. Fourier Transform Infrared (FT-IR) spectra showed a change in intensities of OH groups and CH2 asymmetric stretching vibration after addition of gold nanoparticles, these changes were attributed to the interaction between polymeric matrix and Au NPs. Scanning electron microscopy (SEM) exhibited the partial compatibility between the polymer blend and the Au NPs. Differential scanning calorimetry (DSC) measurement indicated miscibility between the two polymers. The electrical properties were investigated via DC electrical conductivity, where found electrical conductivity increased as Au NPs content increased. The results suggest the choice of Au NPs as filler to enhance the electrical, optical, and thermal properties of PEO/starch blend.