The nucleation and growth mechanism of aluminum oxide (Al2O3) in the early stages of atomic layer deposition (ALD) on monolayer epitaxial graphene (EG) on silicon carbide (4H–SiC) has been investigated by atomic force microscopy (AFM), conductive-atomic force microscopy (C-AFM) and Raman spectroscopy. Differently than for other types of graphene, a large and uniform density of nucleation sites was observed in the case of EG and ascribed to the presence of the buffer layer at EG/SiC interface. The deposition process was characterized by Al2O3 island growth in the very early stages, followed by the formation of a continuous Al2O3 film (∼2.4 nm thick) after only 40 ALD cycles due to the islands coalescence, and subsequent layer-by-layer growth. The electrical insulating properties of the deposited ultrathin Al2O3 films were demonstrated by nanoscale current mapping with C-AFM. Raman spectroscopy …