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The title compound {systematic name: tetra­kis(μ‐3,5‐dinitro­benzoato‐κ2O:O′)bis­[(3,7‐dihydro‐1,3,7‐trimethyl‐1H‐purine‐2,6‐dione‐κO2)copper(II)]}, [Cu2(C7H3N2O6)4(C8H10N4O2)2], consists of paddle‐wheel dimeric tetra­kis(μ‐3,5‐dinitro­benzoato‐κ2O:O′)dicopper(II) units with O‐coordinated caffeine mol­ecules in both apical positions. The entire dimeric mol­ecule lies on a tetra­gonal inversion axis, and thus one nitro­benzoate anion with one Cu atom in a special position belong to the independent part of the mol­ecule. The caffeine ligand bonded to the Cu atom is disordered on a local twofold non‐crystallographic axis coincident with the axis. A π–π stacking inter­action is observed between the caffeine rings and adjacent symmetry‐related benzene rings of the 3,5‐dinitro­benzoate anions.

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