Three-dimensional (3D) graphene-based architectures can combine the two-dimensional properties of graphene with the high surface-to-volume ratio required for a large variety of technological applications. We present a spectro-microscopy study of stable microporous 3D few-layer graphene structures with a very low density of defects/edges and of unsaturated bonds, as deduced by Raman and core level photoemission spectroscopy. These qualities make these interconnected graphene networks ideal candidates to accommodate lithium adatoms, with a high density of Li per unit volume and a Li uptake per C atom higher than the value observed for graphite, as confirmed by core level photoemission spectroscopy.