Porous graphene nanostructures are of great interest for applications in catalysis and energy storage. However, the fabrication of three-dimensional (3D) macroporous graphene nanostructures with controlled morphology, porosity and surface area still presents significant challenges. Here we introduce an ice-templated self-assembly approach for the integration of two-dimensional graphene nanosheets into hierarchically porous graphene nanoscroll networks, where the morphology of porous structures can be easily controlled by varying the pH conditions during the ice-templated self-assembly process. We show that freeze-casting of reduced graphene oxide (rGO) solution results in the formation of 3D porous graphene microfoam below pH 8 and hierarchically porous graphene nanoscroll networks at pH 10. In addition, we demonstrate that graphene nanoscroll networks show promising electrocatalytic activity for the oxygen reduction reaction (ORR).