Two new enantiomeric pure amidinates N,N’-bis-((R)-1-cyclohexylethyl)benzamidinate ((R)-CEBA)- and N,N’-bis-((S)-1-phenylethyl)acetamidinate ((S)-PEAA)- were synthesized by two different synthetic pathways. The chiral amidine (R)-HCEBA was synthesized via the so-called imidoylchloride route. The corresponding lithium derivative (R)-LiCEBA was best obtained by deprotonation of the amidinate hydrochloride (R)-HCEBA·HCl. In contrast (S)-LiPEAA was most efficiently accessed by reaction of methyllithium with bis-((S)-1-phenylethyl)carbodiimide. Further reactions of these lithium salts with LuCl3 in a 2:1 ratio resulted in the enantiomeric pure bisamidinate lutetium complexes [{(R)-CEBA}2Lu-μ-Cl]2 and [{(S)-PEAA}2LuCl(thf)], which are either dimeric or monomeric in the solid state.