A process for producing a bulk highly oriented graphene structure, comprising: (a) preparing a graphene oxide dispersion having graphene oxide (GO) sheets dispersed in a fluid medium; (b) dispensing and depositing the dispersion onto a surface of a supporting substrate to form a layer of GO, wherein the dispensing and depositing procedure includes subjecting the dispersion to an orientation-inducing stress; (c) removing the fluid medium to form a dried layer of GO having an inter-plane spacing d002 of 0.4 nm to 1.2 nm; (d) slicing the dried layer of GO into multiple pieces of dried GO and stacking at least two pieces of dried GO to form a mass of multiple pieces of GO; and (f) heat treating the mass under an optional first compressive stress to produce the highly oriented graphene structure at a first heat treatment temperature higher than 100° C. to an extent that an inter-plane spacing d002 is decreased to a value less than 0.4 nm.