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X-ray absorption near edge spectra provide unique information about the local atomic and electronic structure of the probed atoms and can be used to identify and characterize the surface faceting of nanocrystals (NC) and the bonding nature of ligand-NC interactions.We study the Se K-edge of PbSe and CdSe nanocrystals to understand how different ligands induce various atomic and electronic distortions.We find that encapsulation of PbSe by oleic acid leaves the rocksalt crystal structure undistorted, but certain transition metal complexes lead to tetrahedral distortions with clear spectral signatures.