Abstract Cross‐electrophilic coupling of various benzyl sulfonium salts with C allyl −O electrophiles is described using a simple Co−Mn catalytic system. This catalytic system is able to activate both the stable C sp 3 −S bond of sulfonium salts and the C sp 3 −O bond of allylic acetate or ether under mild reaction conditions to form various functionalized alkyl olefinic compounds. Allyl methyl ethers were employed for the first time in transition metal‐catalyzed cross‐electrophilic coupling to build C sp 3 −C sp 3 bonds. Preliminary mechanistic studies suggested the involvement of benzyl radicals generated from C−S bond cleavage through a single electron transfer.