Three chiral carbonyl hypoiodites, R-C(O)OI, have been prepared from N-protected (S)-valine to give the ligand-stabilised (S)-valinoyl hypoiodite complexes with 4-dimethylaminopyridine, 4-pyrrolidinopyridine, and 4-morpholinopyridine as the stabilising ligands. The identity of the complexes was established by NMR (1H, 13C, 1H-15N HMBC) and single crystal X-ray diffraction analysis.