A new series of Zn(II) complexes were prepared with Schiff bases ligand derived by condensation of 2-tosylamonobenzaldehide with various aminoalcohols. The local atomic structure around Zn atoms in complexes was determined by EXAFS. The electronic absorption spectra, photoluminescence, and biological activities of the complexes were investigated. Display omitted The synthesis of a series of zinc(II) complexes with Schiff bases products of condensation of 2-tosylamonobenzaldehide with various aminoalcohols containing aliphatic spacers of a variable length (CH2)n (n = 2–6) was performed. All compounds were characterized with C, H, N elemental analysis, FT-IR, 1H NMR, X-ray absorption spectroscopy, UV–Vis and photoluminescence data. The local atomic structures of complexes were determined by X-ray absorption spectroscopy from analysis of EXAFS and XANES of Zn K-edges. The electronic absorption spectra, photoluminescence, and biological activities of the complexes were investigated. The assignments of the experimental UV–Vis spectra of zinc(II) complexes have been carried out by Time-Dependent Density Functional Theory TD-DFT calculations.