An experimental and theoretical study of the heteroleptic divalent germanium compounds containing the bidentate coordinating monoanionic β-diketiminate ligand L2GeΣ (L2 = PhNC(Me)CHC(Me)NPh; Σ = Cl (1), I (2), Me (3), OMe (4)) has been performed in this contribution. The new stable germanium(II) compounds 3 and 4 have been synthesized by reaction of 1 with RLi (R = Me, OMe) and fully characterized