Sb2S3 chalcogenide Nanopowder was prepared at low temperatures using the chemical co-precipitation method. PVA/PVP polymeric sheets have been prepared with a constant ratio of 2:1 as a host matrix to incorporate Sb2S3 NPS with a ratio of 0, 1, 3, and 5 wt% via solution casting technique. The X-ray diffraction (XRD) pattern revealed that the prepared Sb2S3 powder belongs to an orthorhombic crystalline structure as a major phase, with a crystal size of 24 nm. The microstructure of the powder as well as 5 wt% Sb2S3/PVA/PVP was investigated using the transmission electron microscope. The Fourier transform infrared spectra of the prepared sheets revealed the success of the interaction between the filler Sb2S3 material with the PVA/PVP as a polymer host matrix. The transmission and reflection spectra of the polymeric Sb2S3 /PVA/PVP sheets measured in the wavelength range 200–2500 nm have been used to calculate the optical band gap energy and refractive index as a function in the Sb2S3 wt%. The Tauc model and the absorption spectrum fitting model were employed to accurately determine the variation of the optical band gap value with Sb2S3 filler percent. Wemple-DiDomenico single-oscillator and Spitzer-Fan, models were applied to analyze the refractive index as a function of the Sb2S3 filling wt%, whereby the dispersion parameters, $${E}_{d},{E}_{o}$$
E
d
,
E
o
as well as the optical high-frequency dielectric constant, $${\varepsilon }_{L}$$
ε
L
carrier concentration to the effective mass ratio, $$N/{m}^{*}$$
N
/
m
∗
were evaluated. A graphical representation of the optical conductivity was also present. The obtained data indicate the possibility of using the prepared Sb2S3/PVA/PVP nanocomposite sheets for optoelectronic applications and optical devices.