In this study, the functional polymers containing heterocyclic ligands were synthesized by microwave modification of a crosslinked poly(vinylbenzyl chloride–divinylbenzene) matrix with 4-tert-butylpyridine, pyrrolidine, and 3-morpholinopropylamine. The sorbents were used to recover Ag(I) from the synthetic and real chloride solutions (4.00 mol/dm3 of NaCl, 0.100 mol/dm3 of HCl). The best Ag(I) sorption was achieved from synthetic and real chloride solutions in the case of pyrrolidine resin (16.2 and 16.7 mg/g, respectively). The sorption kinetic data were well fitted to the pseudo-first-order kinetic model. The degree of silver desorption was approximately 90% using a 1.0% potassium cyanide solution in a 0.50% hydrogen peroxide solution. All resins showed good selectivity for Ag(I) compared to Cu(II), Pb(II), Co(II), Ni(II), and Zn(II) in real chloride solution. On the basis of this study, it can be concluded that the obtained sorbents can be used to recover Ag from various sources such as ores, wastewater, and jewelry scraps.