We report on a spatial mapping of the electronic and vibrational structure of three-dimensional (3D) nanoporous graphene architectures, which have a hierarchical pore structure. We demonstrate that the topology, curvature, and pores lead to local changes in the electronic and vibrational structure and in the hybridization states of the carbon atoms (sp2 vs. sp3-like). Nitrogen substitutions in pyrrolic bonding configurations also contribute to local distortions of the planar geometry of graphene. The distortions influence the electronic density of states at the Fermi level by shifting the Dirac cone apex, opening potential avenues for applications of two-dimensional graphene in 3D devices. Display omitted