Graphical AbstractThe 'S' atom of thiourea functionalized polystyrene adsorbent exhibited very strong interaction with excellent separation of antimony(III and V) ions in presence of large concentration of cobalt and zirconium ions. Abstract 1 A thiourea functionalized polystyrene adsorbent (TPS-DVB) is theoretically and 2 experimentally investigated for selective sorption of antimony from acidic aqueous mixtures 3 with CoCl 2 and ZrOCl 2 . The optimal uptake of 35.6 and 24.2 mg.g -1 , respectively, was obtained 4 for antimony(III) and antimony(V), at pH 1. The isotherm data could be well explained by the 5 Langmuir model and the adsorption kinetics was successfully fitted in the pseudo first-order 6 kinetics. Very high separation factors of 1129 and 918 were achieved for the Sb(III)/Co(II) and 7 Sb(V)/Co(II) mixtures, respectively. The adsorption of Sb(III) and Sb(V) ions onto the TPS-8 DVB adsorbent was explored using the Density Functional Theory (DFT). These theoretical 9 studies of metal coordination with the sulfur atom in the isothiourea group of the adsorbent 10 showed stronger interaction of Sb(III) and Sb(V) ions over Co(II) and ZrO(II) ions. The 11 inclusion of solvation model in the theoretical calculations improved the agreement between the 12 experimental and the calculated metal-sulphur bond distances.13 14