To eliminate the radioisotope 137Cs+ from contaminated water, various inorganic ion-exchange materials have been developed. Many selective ion-exchange materials are relatively expensive and difficult to prepare, whereas conventional materials such as aluminosilicate zeolites lack ion-exchange selectivity in the presence of competing cations. Here, we report a simple but powerful strategy to significantly increase the Cs+ selectivity of conventional zeolites. We demonstrate that encapsulation of elemental sulfur in the micropores of zeolites (NaA, NaX, chabazite, and mordenite) via vacuum sublimation can remarkably increase the selectivity toward Cs+ in the presence of competing ions. It appears that the elemental sulfur does not provide additional adsorption sites for Cs+ ions but increases the ion-exchange selectivity toward Cs+ by providing additional interaction. Various analyses show that sulfur partially donates its electron to the ion-exchanged Cs+ cations in zeolites, indicating significant Lewis acid–base interaction. According to the hard soft acid base (HSAB) theory, the enhanced Cs+ ion-exchange selectivity can be explained by the fact that sulfur, a soft Lewis base, interacts more strongly with Cs+, which is a softer Lewis acid than other alkali and alkaline earth metal cations. Because of the high intrinsic Cs+ selectivity of bare zeolites and selectivity enhancement resulting from sulfur encapsulation, the sulfur-modified chabazite and mordenite showed highly promising Cs+ capture ability in the presence of various competing ions.