The title compound, [Cu(C(4)H(10)NO)I(C(4)H(11)NO)], was obtained unintentionally as the product of an attempted synthesis of a Cu/Zn mixed-metal complex using zerovalent copper, zinc(II) oxide and ammonium iodide in pure 2-(dimethyl-amino)-ethanol, in air. The mol-ecular complex has no crystallographically imposed symmetry. The coordination geometry around the metal atom is distorted square-pyramidal. The equatorial coordination around copper involves donor atoms of the bidentate chelating 2-(dimethyl-amino)-ethanol ligand and the 2-(dimethyl-amino)-ethano-late group, which are mutually trans to each other, with four approximately equal short Cu-O/N bond distances. The axial Cu-I bond is substanti-ally elongated. Inter-molecular hydrogen-bonding inter-actions involving the -OH group of the neutral 2-(dimethyl-amino)-ethanol ligand to the O atom of the monodeprotonated 2-(dimethyl-amino)-ethano-late group of the mol-ecule related by the n-glide plane, as indicated by the O⋯O distance of 2.482 (12) Å, form chains of mol-ecules propagating along [101].