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The interest in graphene stems from its unique band structure that photoemission spectroscopy can directly probe. However, the preparation method can significantly alter graphene's pristine atomic structure and in turn the photoemission spectroscopy spectra. After a short review of the observed band structure for graphene prepared by various methods, we focus on graphene grown on silicon carbide. The semiconducting single crystalline hexagonal SiC provides a substrate of various dopings, where bulk bands do not interfere with that of graphene. Large sheets of high structural quality flat graphene grow on SiC, which allows the exact same material to be used for fundamental studies and as a platform for scalable electronics. Moreover, a new graphene allotrope (multilayer epitaxial graphene) was discovered to grow on the 4H-SiC C-face by the confinement controlled sublimation method. We will focus on the electronic structure of this new graphene allotrope and its connection to its atomic structure.