Solid-state (SS)NMR techniques were applied to characterize the atomic-scale structures of ordered mesoporous carbon (OMC) materials prepared using Pluronic F127 as template with resorcinol and formaldehyde as polymerizing precursors. A rigorous quantitative analysis was developed using a combination of ¹³C SSNMR spectra acquired with direct polarization and cross polarization on natural abundant and selectively ¹³C-enriched series of samples pyrolyzed at various temperatures. These experiments identified and counted the key functional groups present in the OMCs at various stages of preparation and thermal treatment. The chemical evolution of molecular networks, the average sizes of aromatic clusters and the extended molecular structures of OMCs were then inferred by coupling this information with the elemental analysis results.