The synthetic process to obtain triacylgermenolates with alternated counterions by single-electron-transfer reactions or by a direct approach is described. The formation of these derivatives was confirmed by NMR spectroscopy and UV–vis spectroscopy. Moreover, metal–metal exchange reactions of potassium-substituted triacylgermenolate 2a with MgBr 2 , ZnCl 2 , and HgCl 2 are presented. Additionally, 2a was reacted with n Bu 4 NBr, which led to the formation of ammonia-substituted triacylgermenolate 8 . Furthermore, we reacted 2a with HCl/Et 2 O to obtain triacylgermane 9 . Subsequently, we investigated the reaction of 9 with t Bu 2 Zn and t Bu 2 Hg. NMR spectroscopy, single-crystal X-ray crystallography, and UV–vis spectroscopy are employed for analysis of structural properties.