The functional polymer containing heterocyclic ligands was synthesized by microwave modification of a crosslinked poly(vinylbenzyl chloride–divinylbenzene) matrix with thiomorpholine. The modification yield was 89.3%. The sorbent was used to recover Ag(I) from the synthetic and real chloride solutions. The maximum sorption capacity of Ag(I) was approximately 180 mg Ag/g. The sorption kinetic data were well-fitted to the pseudo-first-order kinetic model. The degree of silver desorption was approximately 50.0% using a 1.0% potassium cyanide solution in a 0.50% hydrogen peroxide solution. The resin retained its capacity toward Ag(I) in five consecutive sorption/desorption cycles. The thiomorpholine modified resin was highly selective toward Ag(I) in relation to Cu(II), Pb(II), Co(II), Ni(II), and Zn(II) from the real chloride leaching solution.