The surface structure of nanocrystals (NC) strongly impacts their chemical and optolectronic properties because of their large surface area to volume ratios. However, techniques that can provide experimental atomic-level surface structures of NC are lacking. Here, we show how magic angle spinning (MAS) dynamic nuclear polarization (DNP) solid-state NMR spectroscopy can be used to determine the surface structures of some of the most widely investigated nanocrystals, zinc blende CdSe NCs with spheroidal and plate morphologies.^[1] 1D ¹¹³Cd and ⁷⁷Se cross-polarization magic angle spinning (CPMAS) NMR spectra reveal distinct signals from Cd and Se atoms on the surface of the nanoparticle, and those residing in bulk-like environments below the surface. ¹¹³Cd magic-angle-turning NMR experiments identifies CdSe₃O and CdSeO₃ coordination environments from {111} facets and CdSe₂O₂ coordination environments from {100} facets, where the oxygen atoms are from coordinated oleate ligands. The sensitivity gains from DNP enables acquisition of natural isotopic abundance 2D homonuclear ¹¹³Cd and ⁷⁷Se and heteronuclear ¹¹³Cd-⁷⁷Se correlation solid-state NMR experiments. 2D homonuclear ¹¹³Cd and ⁷⁷Se correlation spectra reveal the connectivity of the surface and core Cd and Se atoms. Importantly, ⁷⁷Se{¹¹³Cd} scalar heteronuclear multiple quantum coherence (J-HMQC) experiments illustrate the connection between the various Cd and Se environments and can be used to selectively measure one-bond ¹¹³Cd-⁷⁷Se scalar coupling constants (¹J_Se-Cd). With knowledge of ¹J_Se-Cd, ⁷⁷Se{¹¹³Cd} heteronuclear spin echo (J-resolved) NMR experiments are then used to determine the number of Se atoms bonded to Cd atoms, and vice versa. The J-resolved experiments directly confirm that major Cd and Se surface species have CdSe₂O₂ and SeCd₄ stoichiometries, respectively. Considering the crystal structure of zinc blende CdSe and the NMR data obtained from NC with spheroidal and platelet morphologies, we conclude that the surface of the spheroidal CdSe nanocrystals is primarily composed of {100} and {111} facets. We will also present preliminary data showing how these methods can be used to probe the surface structure of ligand exchanged CdSe nanocrystals that are passivated with phosphine, amine and chloride ligands. The methods outlined here will be generally applicable to obtain detailed surface structures of a wide variety of main group semiconductors.