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Atomically resolved scanning tunneling microscopy (STM) results are shown for substitutionally doped boron atoms in the hexagonal carbon network of highly oriented pyrolytic graphite (HOPG). STM images of boron-doped HOPG reveal not only a clear change in the electronic structure of the surface graphene network, but also one that directly affects the electronic structure of the graphene layer from the HOPG surface which is very exceptional for STM measurements. The boron atom site in the graphene network appears as the brightest area in the image including the six adjacent carbon atoms which have relatively higher intensity than normal carbon atoms in the STM image. The average boron-to-boron distance in the basal plane is consistent with Raman spectroscopy results. These structural results suggest that the graphite planes can be tailor made both atomically and electronically, and that boron doping can contribute to controlling the properties of the hexagonal carbon network in order to modify its properties relative to those of ideal graphite. © 2001 American Institute of Physics.