Dielectric BaTiO3films were heteroepitaxially grown on Si (100) substrates in cube‐on‐cube manner by employing a conductive TiN buffer layer. An epitaxial TiN film was grown by KrF pulsed excimer laser deposition. BaTiO3film was grown epitaxially on the TiN film at a substrate temperature higher than 600 °C and in an oxygen pressure less than 1 mTorr. This epitaxial BaTiO3/TiN layer on Si was observed to have sharp interfaces and little interdiffusion of constituent atoms by secondary ion mass spectrometry. The surface of the BaTiO3film had a root‐mean‐square roughness less than 1 nm as observed by atomic force microscopy. A TiN/BaTiO3/TiN trilayer structure was formed and the dielectric property was measured for this metal‐insulator‐metal type capacitor. The BaTiO3film showed a high relative dielectric constant of 803 at the frequency of 1 MHz and a low leakage current less than 10−8A/cm2at 2 V. ©1995 American Institute of Physics.