The present study aims to synthesize new copper(II) complexes in the presence of maltol, sodium saccharin and 3-hydroxyflavone. Characterization of the structure of Cu(II) complexes was carried out by FT-IR, CHN analysis and X-ray crystallography. Methods including fluorescence spectroscopy and molecular docking methods were applied to investigate the interaction of copper(II) complexes with human serum albumin. The cytotoxicity of complexes was screened for antiproliferative activity against human breast cancer cells (MCF-7), andcis-platin used as a comparative standard by MTT assay. The experimental results indicated that the fluorescence quenching of HSA by complexes 1-5 was a static quenching. Also, the results showed that complex 3, [Cu(saccharin)(bpca)(H2O)], has higher cytotoxicity compared to other compounds andcis-platin.