As an integration of Pb-free ferroelectrics with wide-gap semiconductors, (Pr, Mn)-codoped BiFeO3 (BPFM)/B-doped diamond layered structure was fabricated on a diamond substrate. B-doped diamond films were homoepitaxially grown on (100) diamond substrate using microwave plasma-enhanced chemical vapor deposition. Then, BPFM thin films were deposited on the B-doped diamond layer by pulsed laser deposition. BPFM thin films were polycrystalline with random orientations on the B-doped diamond layer. Fabricated heterostructure showed saturated P-E hysteresis curves at room temperature. The remnant polarization and the coercive field for maximum electric field of 1000 kV/cm were 60 mu C/cm(2) and 480 kV/cm, respectively. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3568838] All rights reserved.