Bismuth ferrite (BiFeO₃, BFO) is highly regarded for its high-temperature ferroelectric and magnetic properties, making it ideal for advanced applications such as ferroelectric photovoltaic devices. This study aims to enhance BFO’s performance by doping it with zirconium (Zr) cations. Thin films of both undoped and Zr-doped BFO were prepared using the sol–gel method and spin-coated onto fluorine-doped tin oxide (FTO) substrates. X-ray diffraction (XRD) confirmed the films retained a rhombohedral crystal structure, while UV–Visible (UV–Vis) spectroscopy indicated high transparency and a direct band gap. Notably, the band gap narrowed with Zr doping, improving the material's suitability for visible light applications. Ferroelectric measurements revealed that Zr doping led to increased saturation polarization, coercive field, and remnant polarization in the films. Photoconductivity tests further demonstrated that Zr-doped films exhibited reduced leakage current densities, attributed to the co-doping effect, enhancing the films efficiency for photovoltaic applications. These findings highlight the significant improvements in optical and ferroelectric properties of Zr-doped BFO films, making them crucial for the advancement of photovoltaic technology. By combining improved optical transparency and enhanced ferroelectric characteristics, Zr-doped BFO films represent a promising avenue for developing high-performance ferroelectric photovoltaic devices. This research underscores the potential of Zr-doped BFO in contributing to next-generation photovoltaic technologies, paving the way for more efficient energy harvesting and utilization. The integration of Zr-doped BFO films in photovoltaic systems could lead to substantial advancements in energy efficiency and the development of innovative energy solutions.