The cationic complex of ytterbium {[Yb(THF) 6 ] 2 + [(Ph 3 Ge) 2 Cu] - 2 } 2THF (1) was synthesized by redox transmetallation reaction of Yb with Ph 3 GeCu(PPh 3 ) 3 in the presence of a catalytic amount of YbI 2 (THF) 4 and by the exchange reactions of (Ph 3 Ge) 2 Yb(THF) 4 with Ph 3 GeCu(PPh 3 ) 3 or PhC≡CCu. X-ray diffraction study has shown that crystals of 1 have an ionic structure composed of isolated [Yb(THF) 6 ] 2 + cations (Yb-O 2.350(5), 2.369(4), 2.383(5) 9) and [(Ph 3 Ge) 2 Cu] - anions (Cu-Ge 2.335(1), 2.339(1) 9; GeCuGe 175.96(5)°). The Yb and Cu atoms in 1 have distorted octahedral and linear coordinations respectively.