The flourishing environmental concerns have grabbed the attention of researchers developing environmentally supportive materials in various fields. A green approach was used to create biopolymer blend composites based on polyvinyl alcohol (PVA) and chitosan (CS) doped with various concentrations of grape seed (GS). Various analytical techniques, such as Fourier-transform infrared spectroscopy (FTIR), UV–visible (UV) spectra, field emission scanning electron microscope (FE-SEM) and differential scanning calorimetry (DSC) were used to evaluate the optical, structural and thermal properties of the prepared blend composites. The optical properties of blend composites were determined by UV spectroscopy and the findings revealed that absorption intensity increased with increasing GS, while bandgap energy decreased from 4.18 eV for pure blend to 2.91 eV for blend/15 wt% GS. The homogeneous distribution of GS particles in the biopolymer blend was identified with FE-SEM images. DSC results showed that increasing the GS content increased the glass transition temperature of the blend composites. The AC conductivity and dielectric constant were measured using the LCR meter. The conductivity rises with increasing frequency and dosage of GS, with the greatest conductivity obtained at 15 wt% loading. In comparison to a pure blend, it was discovered that the inclusion of 15 wt% GS enhanced the tensile strength by 50%, hardness by 17% and the reduction in elongation at break by 19 %. As a consequence, environmentally friendly PVA/CS/GS biopolymer blend composites with excellent mechanical, thermal, electrical, and dielectric parameters might be a viable green option for flexible electronic, electrochemical and energy storage devices.