The synthesis and characterization of a mixed carboxylate paddle-wheel copper complex, with formula [Cu(μ- Pip)(μ-MeCO2)(MeOH)]2 (Pip = piperonylate or 1,3-benzodioxole-5-carboxylate and MeCO2 = acetate), is here reported. The described compound is a binuclear complex, each pair of similar carboxylate ligands occupyingmutually trans bridging positions,while the methanol occupies the apical positions. The dimers are arranged into 2D layers in the bc plane through a network of O-H⋯O hydrogen bonds established between themethanol and the acetate ligand. Magnetic studies showed a strong antiferromagnetic Cu⋯Cu interaction (J = −308 cm−1), in agreement with the presence of four μ-κO-κO′ carboxylates bridging the metallic centers in the binuclear complex.