The local structure of carbon spheres obtained via the hydrothermal carbonization process is characterized by using a combination of advanced solid-state 13C NMR techniques. Glucose was chosen as the starting product because it offers the possibility of 13C isotopic enrichment and is regarded as a model compound for more complex polysaccharides and biomass, as reported in recent studies. A number of 13C solid-state MAS NMR techniques (single-pulse, cross-polarization, inversion recovery cross-polarization, INEPT, 13C−13C proton-driven magnetization exchange, and 13C−13C double-quantum−single-quantum correlation experiments) were combined to retrieve information about binding motifs and C−C closest neighbor relations. We found that the core of the carbonaceous scaffold is composed of furan rings cross-linked by domains containing short keto-aliphatic chains instead of otherwise expected graphene-type sheets, as mainly reported either for hydrothermal carbon spheres or for biomass-related carbons obtained by low-temperature (<350 °C) pyrolysis treatment.