The molecular and crystal structure of three organogermanes Cl 3 GeCH 2 OC(O)R (where R=–NHC 6 H 11 , –C 10 H 15 , and –NH 2 ) has been determined by X-ray diffraction method in order to investigate geometrical regularities of these molecules. The nature of Ge–O bonding in these molecules was investigated by quantum chemistry method. It was shown that the influence of the nature of ligand, attached to carbon atom of the carbonyl group, on Ge⋯O interatomic distance is incidentally small in isolated molecule while in the crystal it is much more pronounced due to the crystal packing effect. The nature of Ge⋯O bonding corresponds to intermediate type of interatomic interaction in terms of “Atoms in molecules” theory.