A CuAu38 bimetallic nanocluster was synthesized by adding a single copper atom to the Au38(2-PET)24 nanocluster. The absence of CuxAu38(2-PET)24 doped species was demonstrated by MALDI-TOF mass spectrometry. A separation of bimetallic clusters was attained for the first time where isomers of the E2 enantiomer of the Au38Cu1(2-PET)24 adduct were successfully isolated from their parent cluster using chiral HPLC. The CD of the isolated isomers revealed a change in their electronic structure upon copper addition. The luminescence of the Au38Cu1 adduct is significantly enhanced in comparison with the parent Au38 nanocluster. The stability of the newly formed adduct is strongly dependent on the coexistence of the Au38 nanoclusters.