A comparative investigation of graphene prepared by cracking of propylene (C₃H₆) on nickel surfaces with different orientations, Ni(111) and Ni(100), has been carried out using angle-resolved photoemission spectroscopy. It has been shown that the graphene formed on the Ni(111) surface is well ordered on a large surface area, whereas the graphene on the Ni(100) surface has a well-defined domain structure. It has been found that the electronic structures of the two systems are similar to each other, and graphene is strongly bound to the nickel substrate. It has been demonstrated that the intercalation of a gold monolayer for the two systems leads to the formation of an electronic structure that is characteristic of quasi-free-standing graphene.