The nacnac Cu(I) compound [LCu(MeCN)] (2) (L = [{N-(C 6 H 3 Me 2 -2,6)C(Me)} 2 CH] − ) was reacted with complexes containing aromatic cyclo-E 5 ([Cp*Fe(η 5 -E 5 )], E = P (1a), As (1b), Cp* = η 5 -C 5 Me 5 ), cyclo-P 4 ([Cp‴Co(η 4 -P 4 )] (3), Cp‴ = η 5 -C 5 H 2 t Bu 3 ) and cyclo-E 3 ligands ([Cp‴Ni(η 3 -E 3 )], E = P (4a), As (4b)) yielding the heterometallic complexes [(Cp*Fe)(μ,η 5:2 -E 5 )(LCu)] (E = P (5a), As (5b)), [(Cp*Fe)(μ 3 ,η 5:2:1 -E 5 )(LCu) 2 ] (E = P (6a), As (6b)), [(Cp‴Co)(μ,η 4:2 -P 4 )(LCu)] ( 7), [(Cp‴Co)(μ 3 ,η 4:2:1 -P 4 )(LCu) 2 ] (8), and [(Cp‴Ni)(μ,η 3:2 -E 3 )(LCu)] (E = P (9a), As (9b)). These complexes are rare examples of the coordination of a group 11 metal to aromatic cyclo-E n (E = P, As; n = 3−5) ligands. All products were comprehensively characterized by crystallographic and spectroscopic methods. Their dynamic behavior in solution was studied by VT (variable-temperature) NMR spectroscopy, and their electronic structures were elucidated by DFT calculations.