We report on the growth of Si on c(2 × 2) reconstructed LaAlO3(0 0 1) surfaces at high substrate temperature (700 °C) by molecular beam epitaxy. An initial Volmer-Weber mode is evidenced using reflection high energy electron diffraction (RHEED), X-ray photoelectron diffraction (XPD) and atomic force microscopy. After the deposition of a few monolayers, the islands coalesce. Using X-ray photoelectron spectroscopy, we demonstrate that Si islands exhibit an abrupt interface with the LaAlO3 substrate without formation of silicate or silica. Finally, combined RHEED and XPD measurements show the epitaxial growth of Si with a unique Si(0 0 1)//LaAlO3(0 0 1) and Si<1 0 0>//LAO<1 1 0> relationship.