Disclosed is AA′ graphite with a new stacking feature of graphene, and a fabrication method thereof. Graphene is stacked in the sequence of AA′ where alternate graphene layers exhibiting the AA′ stacking are translated by a half hexagon (1.23 Å). AA′ graphite has an interplanar spacing of about 3.44 Å larger than that of the conventional AB stacked graphite (3.35 Å) that has been known as the only crystal of pure graphite. This may allow the AA′ stacked graphite to have unique physical and chemical characteristics.