CdS nanoparticles (NP), 22 Angstrom, have been synthesized from cadmium 2-ethylhexanoate in DMSO as a uniformly sized dispersion. After ripening, CdS exhibits a sharp excitonic emission peak at 402 nm, while in freshly prepared dispersions a broad trapped emission at 510 nm dominates. By using one- and two-dimensional NMR spectroscopy, the conformation of the stabilizer adsorbed to the NP has been determined. The long hexyl chain of 2-ethylhexanoate ions spreads over the surface of NP whereas the short ethyl end is primarily surrounded by DMSO. Surface modification of CdS with nucleophiles such as 4,4-bipyridine, thiophene, trimethylamine, and thiomolybdate anion results in a partial replacement of the stabilizer and reorientation of the hexyl chain away from the surface. The difference in the degree of replacement and/or conformational changes of 2-ethylhexanoate ion depends on the electron donor activity of the modifier.