The integration of reduced graphene oxide (rGO) with perovskite-based ferroelectric materials offers exciting opportunities to enhance the electrical and optical properties of optoelectronic devices. In this study, rare-earth Gd-doped bismuth ferrite (Gd-BBFT) composites with rGO were synthesized using a robust solid-state method and spun calcination techniques. Their structural, morphological, dielectric, magnetic, and optical properties were systematically investigated. X-ray diffraction (XRD) confirmed a rhombohedral crystal structure (R3c) in both composites, with rGO appearing as a secondary phase. The functional groups in rGO facilitated nucleation, leading to increased grain formation and enhanced grain boundary density. A ferroelectric phase transition was observed in Gd-BBFT/rGO near 250°C, making it suitable for temperature-sensitive electronic applications. Impedance spectroscopy revealed non-Debye relaxation behavior, indicating complex charge transport. Magnetic and electrical remanence confirmed the material's potential for switchable states in multifunctional devices. The incorporation of rGO marginally improved the dielectric, impedance, and optical properties of both composites. The optical bandgap was found to be in the range of 2.0–1.9 eV, suggesting enhanced light-absorption capabilities. These improvements make the Gd-BBFT/rGO composites promising candidates for next-generation electronic and optoelectronic components. The findings from this study provide valuable insights into the design of advanced rGO–perovskite composites with tailored properties for energy storage, electronic, and optical applications.