BiFeO 3 thin films were processed on La0.8Sr0.2MnO3 (LSMO) buffered silicon substrate via chemical solution deposition. Short-wave ultraviolet assisted pyrolysis was conducted in oxygen atmosphere in order to improve microstructure. A fine, homogeneous, and phase-pure grain structure with smooth topography was obtained. X-ray photoelectron spectroscopy analysis indicates diffusion of lanthanum and manganese from LSMO into the BiFeO3 film leading to a diffuse interface. Nevertheless, improved polarization and leakage resistance properties were obtained. For the first time polarization switching was obtained in sol-gel BiFeO3 films using capacitance-voltage (C−V) curves. This has been imputed to homogeneous local electrical properties of the film, corroborated by surface scanning potential microscopy investigations. The leakage current mechanisms were investigated as function of temperature, and could be interpreted in terms of the Frenkel-Poole mechanism with a trap depth of 1.6 eV. Finally, the magnetic properties of the LSMO∕BiFeO3 heterostructure are presented in comparison to those of BiFeO3 on platinized silicon. An exchange coupling between BiFeO3 and LSMO layers is suggested.