  Pristine, single-crystalline graphene displays a unique collection of
remarkable electronic properties that arise from its two-dimensional, honeycomb
structure. Using in-situ low-energy electron microscopy, we show that when
deposited on the (111) surface of Au carbon forms such a structure. The
resulting monolayer, epitaxial film is formed by the coalescence of dendritic
graphene islands that nucleate at a high density. Over 95% of these islands can
be identically aligned with respect to each other and to the Au substrate.
Remarkably, the dominant island orientation is not the better lattice-matched
30^{\circ} rotated orientation but instead one in which the graphene [01] and
Au [011] in-plane directions are parallel. The epitaxial graphene film is only
weakly coupled to the Au surface, which maintains its reconstruction under the
slightly p-type doped graphene. The linear electronic dispersion characteristic
of free-standing graphene is retained regardless of orientation. That a weakly
interacting, non-lattice matched substrate is able to lock graphene into a
particular orientation is surprising. This ability, however, makes Au(111) a
promising substrate for the growth of single crystalline graphene films.
