Three-dimensional graphene networks are emerging as a new class of multifunctional constructs with a wide range of potential applications from energy storage to bioelectronics. Their multifunctional characteristics stem from the unique combination of mechanical properties, electrical conductivity, ultra-low density, and high specific surface areas which distinguish them from any polymer, ceramic or metal constructs. The most pressing challenge now is the achievement of ordered structures relying on processes that are highly controllable. Recent progresses in materials templating techniques, including the advent of three-dimensional printing, have accelerated the development of macroscopic architectures with micro-level-controlled features by rational design, with potential for manufacturing.