N,N‐Diethylcarbamates [NbE(O2CNEt2)3] (E = O, S) have been prepared in high yields by treating NbOCl3 or [NbSCl3(CH3CN)2] with CO2/NHEt2 in toluene at approximately –10 °C. The products were characterized by spectroscopic techniques, elemental analysis and X‐ray diffractometry in the case of [NbO(O2CNEt2)3]. The molecular structure of the latter consists of a niobium centre coordinated to the oxido moiety and six O atoms belonging to bridging and bidentate carbamates, in a slightly distorted pentagonal‐bipyramidal arrangement. The structures of both [NbE(O2CNEt2)3] compounds were reproduced by DFT calculations, which show substantial similarity despite the different nature of the chalcogen atoms.