Graphene, a single layer of carbon atoms bonded in a hexagonal lattice, is simultaneously the thinnest, strongest and stiffest known material, as well as being an excellent conductor of both heat and electricity. Reassembly of individual 2D graphene nanosheets into 3D macroscopic structures such as films, papers or fibers offers immense potentials for many important applications such as structural composites, electrodes for batteries, super-capacitors and fuel cells, stretchable/foldable electronics, photo-catalysts, membranes for gas separator and next generation nano-filtration and desalination technologies. Due to its intrinsically exceptional thermal conductivity, high quality graphene macroscopic structures also show immense potential as heat spreader materials for effective thermal management for high power electronics.