The dimeric complex acetato (η4-cycloocta-1, 5-diene) rhodium (I),[Rh (O2CMe)(η4-cod)] 2 (cod= cycloocta-1, 5-diene), reacts with amino acids [HAA= L-alanine,(S)-2-amino-2-phenylacetic acid (L-phenylglycine), N-methylglycine, and N-phenylglycine] and with the amino alcohol (S)-2-amino-2-phenylethanol to afford the aminocarboxylato (η4-cycloocta-1, 5-diene) rhodium (I) complexes [Rh (AA)(η4-cod)](AA= deprotonated amino acid= aminocarboxylato ligand) and [(S)-2-amino-2-phenylethanol](η4-cycloocta-1, 5-diene)-rhodium (I) acetate,[Rh {(S)-HOCH2–CH (Ph)-NH2}(η4-cod)]-(O2CMe)(V). The complexes are characterized by IR, UV/Vis, 1H/13C NMR and mass spectroscopy. The achiral N-phenylglycine ligand gives a chiral N-phenylglycinato complex [Rh (O2C–CH2–NHPh)(η4-cod)](IV) with the amine nitrogen atom becoming the stereogenic center upon metal coordination. Complex IV crystallizes in the tetragonal, chiral space group P43 and the crystal structure reveals twofold