The structure and properties of small neutral and cationic CrGe_n^0,+ clusters, with n from 1 to 5, were investigated using quantum chemical calculations at the CASSCF/CASPT2 and DFT/B3LYP levels. Smaller clusters prefer planar geometries, whereas the lowest-lying electronic states of the neutral CrGe₄, CrGe₅, and cationic CrGe₅⁺ forms exhibit nonplanar geometries. Most of the clusters considered prefer structures with high-spin ground state and large magnetic moments. Relative to the values obtained for the pure Ge_n clusters, fragmentation energies of doped CrGe_n clusters are smaller when n is 3 and 4 and larger when n = 5. The averaged binding energy tends to increase with the increasing number of Ge atoms. For n = 5, the binding energies for Ge₅, CrGe₅, and CrGe₅⁺ are similar to each other, amounting to ∼2.5 eV. The Cr atom acts as a general electron donor in neutral CrGe_n clusters. Electron localization function (ELF) analyses suggest that the chemical bonding in chromium-doped germanium clusters differs from that of their pure or Li-doped counterparts and allow the origin of the inherent high-spin ground state to be understood. The differential ΔELF picture, obtained in separating both α and β electron components, is consistent with that derived from spin density calculations. For CrGe_n, n = 2 and 3, a small amount of d−π back-donation is anticipated within the framework of the proposed bonding model.