Synthesis and characterization of the new polymeric ion exchangers with thiol and sulfonyl hydroxide groups are presented. These new sorbents were also compared with polymeric microspheres possessing methylenethiol groups on the surface presented previously. The polymeric cation ion exchangers in the form of microspheres were obtained by the suspension-emulsion polymerization tetrafunctional monomer: 2,3-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,3-NAF.DM) with styrene (St). Next, multistage modification introducing sulfur-containing group (thiol or sulfonyl hydroxide or methylenethiol) on the surface of polymeric matrices was made. In order to obtain sulfonyl hydroxide derivatives the matrices were performed as follows: the parent microspheres were treated by H2SO4 (Method I) or with the addition of oleum (Method II). The thiol groups were introduced in a two-stage reaction. In the first stage chlorosulfonation of parent microspheres in the presence of chlorosulfonic acid was carried out. Finally, the reduction of modified microspheres by using SnCl(2)2H(2)O was conducted. The sulfur group content (elemental analysis, scanning electron microscope EDX SEM), thermal properties (thermogravimetric analysis), porous structure as well as the swelling characteristics of the functional beads were examined. The surface texture was also visualized by the AFM method.