Over the time, dinuclear Cu(II) amino alcohol complexes have received particular attention, as building blocks in metallo supramolecular chemistry, as model of copper enzymes and precursors of molecular magnetic and catalytic materials. Recently, there have been reports of Cu(II) triethanolamine (TEA) carboxylate complexes used as a selective catalyst for alkanes oxidation and ferro-/antiferromagnetic behaviour. This study investigates the role of triethanolammonium 4-nitrobenzoate salt (HTEA)(4NB) in the structure formation of new metal complexes, focusing on dialkoxo bridged Cu(II) complex [Cu2(TEA)2(4NB)2]∙2H2O (1) with potential biological activity. The compound consists of centrosymmetric dinuclear units, in which two Cu(II) ions are bridged by two μ:η1 oxo bridges of two TEA anions, adopting a NO5 distorsional tetragonal bipyramidal geometry. Dinuclear complexes are hydrogen-bonded with outer-sphere water molecules by intermolecular O–H⋅⋅⋅O hydrogen bond interactions in a 1D supramolecular chain and further interlinked by C–H∙∙∙π stacking interactions. Figure 1. The molecular structure of 1 (a). Fragment of hydrogen-bonded supramolecular chain (b). Representation of C‒H∙∙∙π stacking interactions between the resulted chains (c). 2D fingerprint plots calculated from the Hirshfeld analysis of different interactions (for all contacts, H∙∙∙H, H∙∙∙O/O∙∙∙H, and H∙∙∙C/C∙∙∙H) The structural investigation indicates that non-covalent intermolecular interactions, such as O‒H∙∙∙O and C‒H∙∙∙π, contribute to the packaging of the components in the crystal, while the Hirshfeld surface and 2D fingerprint graphs quantify these interactions and show their priority.