Single layer graphene and graphene oxide feature useful and occasionally unique properties by virtue of their two-dimensional structure. Given that there is a strong correlation between graphene architecture and its conductive, mechanical, chemical, and sorptive properties, which lead to useful technologies, the ability to systematically deform graphene into three-dimensional structures, therefore, provides a controllable, scalable route toward tailoring such properties in the final system. However, the advent of chemical methods to control graphene architecture is still coming to fruition and requires focused attention. The flexibility of the graphene system and the direct and indirect methods available to induce morphology changes of graphene sheets are first discussed in this review. Focus is then given toward chemical reactions that influence the shape of presynthesized graphene and graphene oxide sheets, from which a toolbox can be extrapolated and used in controlling the spatial arrangement of graphene sheets within composite materials and ultimately tailoring graphene-based device performance. Finally, the properties of three-dimensionally controlled graphene-based systems are highlighted for their use as batteries, strengthening additives, gas or liquid sorbents, chemical reactor platforms, and supercapacitors.