Quantum chemical calculations were applied to investigate the electronic structure of mono-, di-, and tri- lithiated triatomic germanium (Ge3Lin) and their cations (n = 0-3). Computations using a multiconfigurational quasi-degenerate perturbation approach (MCQDPT2) based on complete active space CASSCF wavefunctions, MRMP2 and density functional theory reveal that Ge3Li has a 2A' ground state with a doublet-quartet gap of 24 kcal/mol. Ge3Li2 has a singlet ground state with a singlet-triplet (3A' '-1A1) gap of 30 kcal/mol, and Ge3Li3 a doublet ground state with a doublet-quartet (4A' '-2A') separation of 16 kcal/mol. The cation Ge3Li+ has a 1A' ground state, being 18 kcal/mol below the 3A' state. The computed electron affinities for triatomic germanium are EA(1) = 2.2 eV (experimental value is 2.23 eV), EA(2) = -2.5 eV, and EA(3) = -5.9 eV, for Ge3-, Ge32-, and Ge33-, respectively, indicating that only the monoanion is stable with respect to electron detachment, in such a way that Ge3Li is composed of Ge3-Li+ ions. An atoms in molecules (AIM) analysis shows the absence of a Ge-Ge-Li ring critical point in Ge3Li. An electron localization function (ELF) map of Ge3Li supports the view that the Ge-Li bond is predominantly ionic; however, a small covalent character could be anticipated from the Laplacian at the Ge-Li bond critical point. The ionic picture of the Ge-Li bond is further supported by the natural bond orbital (NBO) results. The calculated Li affinity value for Ge3 is 2.17 eV, and the Li+ cation affinity value for Ge3- amounts to 5.43 eV. The larger Li+ cation affinity of Ge3- favors an electron transfer, resulting in a Ge3-Li+ interaction.