The direct cross-couplings of aryl sulfonium salts with aryl halides could be achieved by using nickel as a reaction catalyst. The reactions proceeded efficiently via C–S bond activation in the presence of magnesium turnings and lithium chloride in THF at ambient temperature to afford the corresponding biaryls in moderate to good yields, potentially serving as an attractive alternative to conventional cross-coupling reactions employing preprepared organometallic reagents.