To evaluate the antioxidant activity of potential synthetic enzyme mimetics, we prepared new five copper(II) complexes via a self-assembly method and named them [Cu(2-(HOCH₂)py)₃](ClO₄)₂ (1), [Cu(2-(HOCH₂)py)₂(H₂O)₂]SiF₆ (2), [Cu₂(2-(HOCH₂CH₂)py)₂(2-(OCH₂CH₂)py)₂](ClO₄)₂ (3), [Cu(pyBIm)₃](BF₄)₂·1.5H₂O (4) and [Cu(py₂C(OH)₂)₂](ClO₄)₂ (5). The synthetic protocol involved N,O- or N,N-donors: 2-(hydroxymethyl)pyridine (2-(HOCH₂)py), 2-(hydroxyethyl)pyridine (2-(HOCH₂CH₂)py), 2-(2-pyridyl)benzimidazole (pyBIm), di(2-pyridyl)ketone (py₂CO). The obtained Cu(II) complexes were fully characterised by elemental analysis, FTIR, EPR, UV-Vis, single-crystal X-ray diffraction and Hirshfeld surface analysis. Crystallographic and spectroscopic analyses confirmed chromophores of both monomeric ({CuN₃O₃} (1), {CuN₂O₄} (2), {CuN₆} (4), {CuN₄O₂} (5)) and dimeric complex ({CuN₂O₃} (3)). Most of the obtained species possessed a distorted octahedral environment, except dimer 3, which consisted of two copper centres with square pyramidal geometries. The water-soluble compounds (1, 3 and 5) were selected for biological testing. The results of the study revealed that complex 1 in solutions displayed better radical scavenging activity than complexes 3, 5 and free ligands. Therefore, complex 1 has been selected for further studies to test its activity as an enzyme mimetic. The chosen compound was tested on the erythrocyte lysate of two groups of patients after undergoing chemotherapy and chemoradiotherapy. The effect of the tested compound (1) on enzyme activity levels (TAS, SOD and CAT) suggests that the selected complex can be treated as a functional mimetic of the enzymes.