A series of novel low valent germanium compounds RN(CHR 2 CR 1 R 3 O)(CHR 4 CHR 5 O)Ge 1–13 (R = Me, Ph, Bn; R 1 , R 2 , R 3 , R 4 , R 5 = H, Me, Ph, (CH 2 ) 3 , (CH 2 ) 4 , CH 2 (C 6 H 4 )) was obtained via the reaction between Ge[N(SiMe 3 ) 2 ] 2 and various dialkanolamines. All new compounds were characterized by elemental analysis, 1 H and 13 C NMR spectroscopy and in several cases by X-ray diffraction analysis (1, 3, 8, 10). The compounds 1, 3, 8 are dimeric in the solid state due to the formation of intermolecular Ge–O bonds, the complex 10 is monomeric, all compounds possess a transannular Ge–N bond. The reactivity of the germylenes synthesized was investigated in reactions of oxidative insertion (with halogenation reagents, MeI, disulfides), [1 + 4]-cycloaddition, oxidation and in reactions with water and acetic anhydride. Some reactions were investigated by DFT calculations.