The quality and crystallinity of ultrathin dielectric layers depend crucially on the details of interface formation and chemical stability. Using a combination of photoelectron (XPS) and electron-energy-loss spectroscopy, low-energy electron-diffraction, and transmission electron microscopy (TEM), we show that crystalline epitaxial layers of Ba2SiO4 can be grown on Si(100) substrates from evaporated Ba in oxygen background atmosphere at 650 °C. Since the silicate is chemically by far more stable than the oxides of Si and Ba, an atomically sharp interface with no interface oxide is formed, as confirmed by XPS and TEM. However, the interface is rough on the atomic scale. dc and frequency-dependent electrical measurements reveal a relative dielectric constant of 22.8, low hysteresis in CV measurements, and low leakage currents but still fairly high interface trap densities. © 2016 American Physical Society.