In this paper composite materials, based on polymer blends of polyvinyl alcohol (PVA): polyvinyl pyrrolidone (PVP) with small optical band gap, has been studied. Silver sulfide (Ag2S) semiconductor particles have been synthesized in PVA:PVP blend host polymer, using in situ method. X-ray diffraction (XRD) analyses and Fourier transform infrared (FTIR) spectroscopy for the composite samples were carried out. From the XRD pattern, distinguishable crystalline peaks caused by the Ag2S semiconductor particles were observed. From the result of FTIR spectroscopy, the intensity of the FTIR bands were shifted and increased, revealing the occurrence of interactions between the PVA:PVP blend system and Ag2S particles. The composite samples were found to exhibit absorption spectra that cover UV–visible to near infrared regions. The absorption edge was found to be 5eV for pure PVA:PVP system and shifted to 1.15eV for incorporated PVA:PVP with 3M of Ag2S. The refractive index was also evaluated for the samples and observed to be increased from 1.15 to 1.52 as doping increased to the highest. A linear relationship between the refractive index and the filler fraction has been reported. Theoretical discussion of optical dielectric loss, which is a crucial parameter for the band gap estimation, was given. The achieved results reveal that spectra of the optical dielectric loss (ɛi) can be used to study the band gap structure and Tauc's model can be important in determining the types of electronic transition. The optical band gap was found to decrease from 5.2eV for the pure PVA:PVP to 1.1eV for doped PVA:PVP with 3M of Ag2S. Such reduction can be associated with the increase of optical dielectric constant. Finally, the correlation between optical dielectric constant and density of states was discussed.