Polyethylene oxide (PEO) and polyvinyl pyrrolidone (PVP) were used to prepare virgin and equimass fraction blend samples via an ordinary solution casting route. Polyblend was filled with a different mass fraction of green biosynthesized metallic gold nanoparticles (AuNP's). The organometallic Nanocomposites were then studied using different characterization techniques. X-ray diffraction (XRD) investigation supports the formation of a face-centered cubic (FCC) structure of AuNP's. FTIR spectral data reveals the persistence of the main vibrational groups in the polymeric matrix and suggests that the complexation process occurs via the carbonyl group. UV/Vis. is measurement used to estimate values of the optical energy gap and confirms the formation of AuNP's in the nano-scale through observation of the surface plasmon resonance (SPR) peak at about 562 nm. Density functional theory (DFT) studies were employed to confirm the suggested mechanism of complexation between constituting polymers and to retrace structural changes within the polymeric matrices. Zeta sizer and transmission electron microscopy (TEM) reveals that AuNP's were polydispersed with sizes ranging from 5-23.1 nm.