Graphene, a two-dimensional sheet of sp2-bonded carbon arranged in a honeycomb lattice, is not only the building block of fullerenes, carbon nano tubes (CNTs) and graphite, it also has interesting properties, which have caused a flood of activities in the past few years. The possibility to grow graphitic films with thicknesses down to a single graphene layer epitaxially on SiC{0001} surfaces is promising for future applications. The two-dimensional nature of epitaxial graphene films make them ideal objects for surface science techniques such as photoelectron spectroscopy, low-energy electron diffraction, and scanning probe microscopy. The present article summarizes results from recent photoemission studies covering a variety of aspects such as the growth of epitaxial graphene and few layer graphene, the electronic and structural properties of the interface to the SiC substrate, and the electronic structure of the epitaxial graphene stacks. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)