A series of germanes Ar 3 GeX, containing electron-withdrawing substituents [Ar = p-FC 6 H 4 , 1a−d, 1a (X = Cl), 1b (X = Br), 1c (X = H), 1d (X = NMe 2 ); p-F 3 CC 6 H 4 , 2a−d, 2a (X = Cl), 2b (X = Br), 2c (X = H), 2d (X = NMe 2 )], was synthesized and used to prepare symmetrical digermanes Ar 3 Ge−GeAr 3 , (p-FC 6 H 4 ) 3 GeGe(C 6 H 4 F-p) 3 (3), and (p-F 3 CC 6 H 4 ) 3 GeGe(C 6 H 4 CF 3 -p) 3 (4) and trigermane [(p-F 3 CC 6 H 4 ) 3 Ge] 2 Ge(C 6 F 5 ) 2 ( 5) by hydrogermolysis reaction. The properties of all compounds were investigated by multinuclear NMR and for oligogermanes by UV/vis and fluorescence spectroscopy, as well as by electrochemical methods. In addition, the molecular structures of 1a, 1b, 2b, 2c, and 3−5 were studied by X-ray diffraction analysis. Compound 5 showed a significantly shifted UV/visible absorption to the red field in comparison with previously described derivatives.