The structural and electrical properties of BiNi 0.5 Mn 0.5 O 3 /LaNi 0.5 Mn 0.5 O 3 (BNM/LNM) and BiNi 0.5 Mn 0.5 O 3 /LaNiO 3 (BNM/LNO) heterostructure thin films fabricated on Pt/Ti/SiO 2 /Si(100) substrates by a chemical solution deposition method were studied. The x-ray diffraction results indicated that polycrystalline hexagonal perovskite structures were formed. It was found that the electrical properties of the heterostructure thin films were obviously different from each other. For the Au/BNM/LNM/Pt structure, slightly distorted ferroelectric hysteresis loops were observed and the leakage current density versus applied electric voltage curves at positive and negative biases were asymmetrical. The conduction mechanism was dominated by an ohmic conduction mechanism at positive bias, whereas at negative bias, the conduction mechanism was dominated by the ohmic conduction mechanism, trapfilled-limit (TFL) conduction, and grain-boundary-limited behavior. However, for the Au/BNM/LNO/Pt structure, slim hysteresis loops with no distortion were observed and the leakage current was approximately four orders of magnitude lower than that of Au/BNM/LNM/Pt. The conduction mechanisms were controlled mainly by an ohmic conduction mechanism, TFL conduction, and grain-boundary-limited behavior at positive and negative biases.