Graphene-based carbon nanostructures with nanometer dimensions have been of great interest due to the existence of a bandgap. So-far, well-ordered edge structure and uniformly synthesized graphene quantum dots (GQDs) with a hexagonal single-crystalline structure have not been directly observed owing to the limited precision of current synthesis approaches. Herein, we report on a novel approach not just for the synthesis of the size-controlled single-crystalline GQDs with hexagonal shape but also for a new discovery on constructing 2D and 3D graphene single crystal structures from n-glucose via catalytic solution chemistry. With size-controlled single-crystalline GQDs, we elucidated the crucial role of edge states on luminescence from the correlation between their crystalline size and exciton lifetime. Furthermore, blue-emissive single-crystalline GQDs were used as an emitter on light-emitting diodes and exhibit stable deep-blue emission regardless of the voltage and doping level.