Well-defined noble metal nanocrystals (NMNCs) of a unique morphology yet a uniform facet have attracted broad interests. In this regard, those with a highly branched architecture have gained particular attention. Most of the currently existing branched NMNCs, however, are enclosed by mixed facets. We now report that branched Au nanoarchitectures could be facilely fabricated by mixing an aqueous solution of KAuCl₄, an aqueous dispersion of graphene oxide, and ethanol under ambient conditions. Interestingly, unilike the conventional branched NMNCs, our unique Au nanostructures are predominately enriched with a uniform facet of {111}. Compared to the spherical Au nanostructures exposed with mixed facets, our branched nanospecies of a uniform facet display superior catalytic performances both for the catalytic reduction of 4-nitrophenol and the electrocatalytic oxidation of methanol. Our investigation represents the first example that Au nanostructures simultaneously featured with a highly branched architecture and a uniform crystal facet could be formulated. Our unique Au nanostructures provide a fundamental yet new scientific forum to disclose the correlation between the surface atomic arrangement and the catalytic performances of branched NMNCs.