Trichlorogermane triethylaminate [HGeCl₃·NEt₃] has been synthesized and its structure investigated using the methods of NMR and IR spectroscopy and quantum chemistry. Possible structures of complexes of triethylamine with trichlorogermane are considered. The presence of two minima on the potential energy surface is shown; the global minimum corresponds to the structure with proton transfer to the nitrogen atom, [Et₃NH]⁺[GeCl₃]^–, while the local minimum lying by 25.8 kcal/mol above is characterized by the presence of very weak van-der-Waals interaction NGe. The comparison of the experimental and calculated chemical shifts of the proton is indicative of the formation of complex with proton transfer to the nitrogen atom in the liquid phase.