Graphical Abstract: The crystalline compounds (Hbipy)2[Ge(HCitr)2]•2H2O (1) and [CuCl(bipy)2]2[Ge(HCitr)2]•8H2O (2) (where H4Citr is citric acid, bipy is 2,2ʹ-bipyridine) were obtained for the first time and their structures were determined by the single-crystal X-ray diffraction method. The two compounds were characterized by IR spectroscopy, thermogravimetric (TGA) and elemental analyses. In both compounds complex bic(citrato)germanate anion is formed, protonated 2,2'-bipyridine molecule and [Cu(bipy)2Cl]+ complex are cations in 1 and 2, respectively.