Potassium complexes of N,N-dialkylhydroxylamines [KONR2, R = Me (1a), Pr-i (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 [((KONPr2)-Pr-i)((HONPr2)-Pr-i)(THF)] 2b. 1b, 2b and [(KONBn2)(6)(THF)(4)] (3) were characterized by NO 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 Pr-i 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 center dot center dot center dot H center dot center dot center dot ONR2) units of 1b and 2b, which is asymmetric in the first and symmetric in the second case.