High-quality thin insulating films on graphene (Gr) are essential for field-effect transistors (FETs) and other electronics applications of this material. Atomic layer deposition (ALD) is the method of choice to deposit high-κ dielectrics with excellent thickness uniformity and conformal coverage. However, to start the growth on the sp2 Gr surface, a chemical prefunctionalization or the physical deposition of a seed layer are required, which can effect, to some extent, the electrical properties of Gr. In this paper, we report a detailed morphological, structural, and electrical investigation of Al2O3 thin films grown by a two-steps ALD process on a large area Gr membrane residing on an Al2O3–Si substrate. This process consists of the H2O-activated deposition of a Al2O3 seed layer a few nanometers in thickness, performed in situ at 100 °C, followed by ALD thermal growth of Al2O3 at 250 °C. The optimization of the low …