A tetranuclear copper(II) complex (1) was synthesized using 2‐hydroxy‐N‐(quinolin‐8‐yl)acetamide ligand. Single‐crystal X‐ray diffraction studies revealed that the complex consists of a distorted Cu4O4 core in which the four copper(II) ions are linked by alkoxo bridges. X‐ray analysis also evidenced intramolecular noncovalent carbonyl–π interactions. Those interactions that are encountered between lone‐pair electrons (of the amide oxygen atoms here) and π* orbitals of aromatic rings, have been recently recognized as important stabilizing interactions (named n→π*Ar). Computational studies using density functional theory (DFT) were conducted to evaluate the structural role of such interactions in the present tetranuclear entity. The magnetic properties of 1 were also investigated and DFT calculations were employed to predict, rationalize and correlate the exchange interactions operating within this original complex. A tetranuclear copper(II) complex with a strongly distorted Cu4O4 core was prepared and its magneto‐structural properties are reported. Density functional theory was used to provide a rationale of the magnetic interactions as well as an estimate of the energy of intramolecular n→π* interactions.