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The doping of graphene to tune its electronic structure is essential for its further use in carbon based electronics. Adapting strategies from classical silicon based semiconductor technology, we use the incorporation of heteroatoms in the 2D graphene network as a straightforward way to achieve this goal. Here, we report on the synthesis of boron-doped graphene on Ni(111) in a chemical vapor deposition process of triethylborane on the one hand and by segregation of boron from the bulk on the other hand. The chemical environment of boron was determined by x-ray photoelectron spectroscopy and angle resolved photoelectron spectroscopy was used to analyze the impact on the band structure. Doping with boron leads to a shift of the graphene bands to lower binding energies. The shift depends on the doping concentration and for a doping level of 0.3 ML a shift of up to 1.2 eV is observed. The experimental results are in agreement with density-functional calculations. Furthermore, our calculations suggest that doping with boron leads to graphene preferentially adsorbed in the top-fcc geometry, since the boron atoms in the graphene lattice are then adsorbed at substrate fcc-hollow sites. The smaller adsorption distance of boron compared to carbon leads to a bending of the graphene sheet in the vicinity of the boron atoms. By comparing calculations of doped and undoped graphene on Ni(111), as well as the respective free-standing cases, we are able to distinguish between the effects that doping and adsorption have on the band structure of graphene. Both, doping and bonding to the surface, result in opposing shifts on the graphene bands.