In this work, Bi₂O₃ nanoflakes (NFs) were synthesized using the co-precipitation method. To understand the crystal structure-surface morphology and their functional properties such as optical band-gap energy, specific capacitance and magnetic properties are examined by various analytical techniques including X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), High-Resolution Transmission Electron Microscopy (HRTEM), Vibrating Sample Magnetometer (VSM), UV–Visible Diffuse Reflectance Spectroscopy (UV-DRS), X-ray Photoelectron Spectroscopy (XPS), Raman Spectroscopy, and Cyclic Voltammetry (CV). FE-SEM confirmed the formation of the nanoflakes, while HRTEM verified their monoclinic crystal structure and provided details on the orientation of the lattice planes. XRD result showed distinctive peaks corresponding to the α-phase, indicating a crystallite size of 8.21 nm. Raman and XPS results are also demonstrated formation of the Bi₂O₃ NFs with their signature bands. VSM analysis revealed the presence of both magnetic and nonmagnetic phases in the Bi₂O₃ NFs. Optical studies indicated a promising band gap of 1.9 eV, suggesting potential for optoelectronic applications. Surface analysis confirmed the composition of Bi⁺ and O2⁻ in the NFs. Additionally, electrochemical assessments through CV demonstrated a significant specific capacitance of 537 F/g at 20 mV/s. Nyquist plot analysis suggested an equivalent circuit R(CR)(CR), indicating an optimal fit. Furthermore, we have made the systematic comparison of optical band gap energy of Bi₂O₃ with reported different nanostructures such as Peanut, needles, rod and flakes and found that the present study nanoflakes offer much lower band energy compared to above mentioned all other morphologies. Due to the obtained lower energy band gap and specific capacitance performance of the Bi₂O₃ NFs, it is strongly suggested to the advanced energy storage applications.