Potassium complexes of N,N-dialkylhydroxylamines [KONR2, R=Me (1a), iPr (2a), CH2C6H5] were synthesized by the deprotonation of the corresponding N, N-dialkylhydroxylamines with KH. 1a and 1b [(KONMe2)(HONMe2)] dissolve in THF under the addition of an additional equiv of the parent hydroxylamine to give 1b and [(KONiPr2)(HONiPr2)(THF)] 2b. 1b, 2b and [(KONBn2)6(THF)4] (3) were characterized by NMR and IR spectroscopy, by elemental analyses, and by X-ray diffraction of single crystals. 1b and 2b crystallize as polymers, whereby compound 1b with smaller groups leads to higher coordination numbers at the potassium atoms (CN=7) and double-stranded more complex ladder-type aggregates, whereas 2b with the larger iPr groups contains potassium atoms with a coordination number of 5 and is a single-stranded polymer. The compound {[KON(CH2C6H5)2]6(THF)4} (3) exists in a hexameric bis-cubane-based form in the solid state. Quantum chemical calculations were undertaken to examine the nature of the hydrogen bonding in the (R2NO...H...ONR2) units of 1b and 2b, which is asymmetric in the first and symmetric in the second case.