Solid-state nuclear magnetic resonance (SSNMR) has been extensively used to characterize molecular structures at atomic scales. [1] Concerning biomolecular applications, structural studies are commonly performed on 13 C and/or 15 N enriched samples to compensate for their low natural abundance (1.11 % for 13 C and 0.37 % for 15 N). However, this strategy is mainly restricted to biomolecules that can be easily isotopically enriched and has proven difficult to expand to other types of systems.To date, only a few examples of natural abundance (NA) 2D 13 C-13 C correlation experiments in solids have been reported using pulse sequences that rely on through-bond polarization transfer. [2] This type of experiment provides onebond connections and is limited to small crystalline molecules, as it requires 2 to 10 days of experimental time. Owing to the low abundance of 13 C nuclei, cross-peak intensities are about four orders of magnitude smaller for experiments performed on NA systems compared to their labeled equivalents.Recently, dynamic nuclear polarization (DNP) performed with a high-power high-frequency microwave source (gyrotron), a low-temperature (LT) magic-angle spinning (MAS) probe, and a suitable polarizing agent has emerged as an appropriate answer to the sensitivity limitation of SSNMR even at high magnetic fields. [3][4][5] This work by Griffin and coworkers has triggered a strong interest in the science community and high-field MAS-DNP has been used on many different types of systems ranging from biological systems [6][7][8] to materials. [9][10][11] Herein we will show that the sensitivity enhancement obtained with DNP can be significant enough to obtain 2D 13 C-13 C NMR correlation spectra on NA microcrystalline solids in 20 min, [12] that is, within an experimental time comparable to experiments routinely performed on isotopically labeled systems.The relevance of performing DNP experiments has so far mainly been judged by comparing the signal-to-noise ratio (S/ N) with and without microwave (MW) irradiation. This "DNP enhancement" (e DNP ) has shown factors of up to 200 at 9.4 T and 100 K, [5,13] but in most applications, a factor of 10 to 20 is obtained. However, we demonstrate here that the effective sensitivity gain in DNP experiments cannot be simply evaluated by measuring e DNP . Instead, we propose using the absolute sensitivity ratio (ASR) to evaluate the relevance of DNP by comparing the S/N per unit time obtained under optimized DNP conditions with the one obtained under standard NMR conditions (potentially using for example larger sample volumes and higher magnetic fields). Previously, Rossini et al. and Vitzthum et al. introduced an overall sensitivity factor [14] and a global DNP factor, [15] respectively, which take into account some of the important parameters. These factors are reduced forms of the ASR and are discussed in more detail in the Supporting Information, S4.One of the main differences between conventional and DNP-enhanced SSNMR experiments is the effective sample volume. For DNP...