This study describes synthesis and structure features of new heterometallic mixed‐ligand cation‐anionic complexes {[Fe(phen)3][Ge2(OH)2(μ‐Tart)2]}2 ⋅ 13H2O(I), [Co(phen)3]2[{Ge2(OH)(H2Tart)(μ‐Tart)2}Cl] ⋅ 11H2O(II), [Ni(phen)3][Ge2(OH)2(μ‐Tart)2] ⋅ 5H2O(III), [Ni(phen)3]2[{Ge2(OH)(H2Tart)(μ‐Tart)2}Cl] ⋅ 11H2O(IV) (Tart ‐ tartaric acid, phen ‐ 1,10‐phenantroline)‐potential drugs, nutritional supplements and growth stimulants. Two forms of tartratogermanate anions are selectively recognized using Fe (II), Co (II), Ni (II) 1,10‐phenantroline cations as receptors. The [Ge2(OH)2(μ‐Tart)2]2− (I, III) contains two Ge atoms bounded by two bridging tartaric acids, the coordination polyhedron of both five‐coordinated Ge atoms is a trigonal bipyramid, while in the [Ge2(OH)(H2Tart)(μ‐Tart)2]3− (II, IV) two Ge atoms have different coordination polyhedrons ‐ trigonal bipyramid and distorted octahedron, formed through the additional terminal tartaric acid. Cations with the common formula [Me(phen)3]2+ (Me=Co, Fe, Ni) form the coordination polyhedron octahedron.