Chemo- and regioselectively nickel-catalyzed reductive benzylarylation of unactivated alkenes with o-bromobenzyl chlorides is disclosed herein, in which electrophiles participate through a single-component double-site approach. Moreover, its utility is underscored by the concise synthesis of bioactive Indane compounds and postreaction functionalizations leading to structurally diverse scaffolds. Preliminary mechanistic investigations suggest a radical chain reaction mechanism.