This research paper describes the fabrication of bionanocomposites (BNCs) based on silk fibroin (SF) and reduced graphene oxide (rGO). The recorded UV–visible (UV–vis) spectra of the sample confirm the reduction of GO to rGO in SF by showing a plasmon resonance band within the wavelength range of 261–268 nm. The X-ray diffraction (XRD) peak at 11.6° corresponding to the GO intensity decreases with increasing reaction time, resulting in rGO in the SF host matrix. The morphological behavior of the SF–rGO BNCs is scrutinized using scanning electron microscopy (SEM), and the images clearly indicate the existence of rGO within the matrix. The increasing amount of GO in the SF shows broken graphene sheets, which can increase the surface roughness and establish a strong physical contact between the SF and rGO nanosheets. The high-resolution transmission electron microscope (HR-TEM) image of the bionanocomposite showed that the formed rGO encompassments of fewer layers are stacked, each with fewer wrinkles and folding. The Raman spectroscopy confirmed the formation of rGO by showing the increased intensity ratio of D to G band (I D/I G) in the bionanocomposite samples. The rGO effect on the electrical conductivity is measured, and the results show that DC conductivity increases from 1.28 × 10–9 to 82.4 × 10–9 S/cm with an increase in the GO content in the SF biopolymer. The investigations demonstrate loss of the insulation property and improved conducting behavior of the SF biopolymer.