Selective adsorption desulfurization of dimethyl disulfide (DMDS) from methyl tert-butyl ether (MTBE) has been studied on the silicalite-1/CuY core-shell composites. Different copper ion sources (CuCl2, Cu(NO3)(2), and CuSO4) were investigated to form CuY as the core by Cu2+ ion-exchange on NaY zeolite. These silicalite-1/CuY core-shell composites were synthesized at the mass ratio of tetraethyl orthosilicate (TEOS)/tetrapropylammonium hydroxide (TPAOH)/ethanol/H2O/CuY = 20 g:19 g:17 g:87 g:5 g. Results showed that the core-shell Y-CuCl2 displayed the best performance in desulfurization of DMDS with a sulfur adsorption capacity of 32.882 mg(s)/g(adsorbent), owing to its significant mass gain and compact coatings after being coated by silicalite-1 on Y-CuCl2. Also, the preparation process of CuY and the shape selective adsorption mechanism of desulfurizing DMDS from MTBE on the silicalite-1/CuY core-shell composites were expounded.