Co-doping of Fe sites in BiFeO3 polycrystalline films effectively suppresses leakage current. Polycrystalline BiFe1–2xMnxCoxO3 and BiFe1–2xTixCoxO3 (x = 0, 0.01, 0.02, 0.03) films were prepared using the sol-gel spin-coating method. A systematic investigation was conducted to determine the impact of (Mn2+/Ti4+, Co2+) co-doping on the structural, leakage current, ferroelectric, dielectric, and optical properties of BiFeO3 films. Results reveal that BiFe1–2xAxCoxO3 (A=Mn2+, Ti4+) films maintain a stable tripartite structure, with (Mn2+/Ti4+, Co2+) co-doping inducing lattice distortion. The leakage current density of BiFe0.98Mn0.01Co0.01O3 (3.45×10−7 A/cm2) and BiFe0.96Ti0.02Co0.02O3 (2.05×10−6 A/cm2) is reduced by 2–3 orders of magnitude relative to pure BiFeO3. Additionally, these films exhibit high remanent polarization values of 188.4 μC/cm2 and 186.8 μC/cm2, respectively. Optical band gaps decrease with (Mn, Co) co-doping and increase with (Ti, Co) co-doping. The magnetic properties are enhanced with increased (Mn, Co) doping but are reduced as (Ti, Co) doping increases. This study provides enhanced understanding of Fe-site co-doping's role in reducing leakage current and improving ferroelectricity in BiFeO3 films, offering valuable insights for photovoltaic applications involving BiFeO3 thin films.