The selective C(sp3)–S bond cleavage of thioethers was first developed to prepare unsymmetrical disulfides by using electrophilic halogenation reagents. In this strategy, NBS (N-bromosuccinimide) achieves selective furfuryl C(sp3)–S bond cleavage of furfuryl alkylthioethers at room temperature. Meanwhile, NFSI (N-fluorobenzenesulfonimide) enables selective methyl C(sp3)–S bond cleavage of aryl and alkyl methylthioethers at an elevated temperature. Notably, the substrate scope investigation indicates that the order of selectivity of the C–S bond cleavage is furfuryl C(sp3)–S > benzyl C(sp3)–S > alkyl C(sp3)–S > C(sp2)–S bond. Moreover, this practical and operationally simple strategy also provides an important complementary way to access various unsymmetrical disulfides with excellent functional group tolerances and moderate to good yields.