The surface structure of organically capped PbS nanocrystals using synchrotron radiation excited core-level photoelectron spectroscopy has been studied. The nanocrystallites prepared by methods of colloidal chemistry have average diameters of 3.1, 3.9, 4.6, and 7.6 nm with narrow size distributions and are stabilized either with oleic acid only or with a combination of trioctylphosphine and oleic acid as ligands. High resolution photoelectron spectroscopy measurements allowed the surface structure to be studied and in particular how the organic ligands bind to the surface of the PbS nanocrystals to be elucidated. The results indicate that the trioctylphosphine ligands passivate only the surface S sites while oleic acid ligands appear to bind mainly to Pb sites.