The 1D Cu(II) coordination polymers [Cu₃(L¹)(NO₃)₄(H₂O)₂]_n (1) and [Cu₂(H₂L²)(NO₃)(H₂O)₂]_n(NO₃)_n (2) have been synthesized using the aroylhyrazone Schiff bases N'¹,N'²-bis(pyridin-2-ylmethylene)oxalohydrazide (H₂L¹) and N'¹,N'³-bis(2-hydroxybenzylidene)malonohydrazide (H₄L²), respectively. They have been characterized by elemental analysis, infrared (IR) spectroscopy, UV-Vis spectroscopy, electrospray ionization mass spectrometry (ESI-MS), single crystal X-ray diffraction and variable temperature magnetic susceptibility measurements (for 2). The ligand (L¹)²⁻ coordinates in the iminol form in 1, whereas the amide coordination is observed for (H₂L²)²⁻ in 2. Either the ligand bridge or the nitrate bridge in 2 mediates weak antiferromagnetic coupling. The catalytic performance of 1 and 2 has been investigated toward the solvent-free microwave-assisted oxidation of a secondary alcohol (1-phenylethanol used as model substrate). At 120°C and in the presence of the nitroxyl radical 2,2,6,6-tetramethylpiperydil-1-oxyl (TEMPO), the complete conversion of 1-phenylethanol into acetophenone occurs with TOFs up to 1,200 h⁻¹.