A new strategy for the construction of chiral sulfides by catalytic enantioselective hydrothiolation of alkenes via an electrophilic pathway has been developed. Using this strategy, cyclic and acyclic unactivated alkenes efficiently afforded various chiral products in the presence of electrophilic sulfur reagents and silanes through chiral chalcogenide catalysis. The obtained products were easily transformed into other types of valuable chiral sulfur-containing compounds. Mechanistic studies revealed that the superior construction of chiral thiiranium ion intermediate is the key to achieving such a transformation.