Herein, a facile and efficient dehalogenative arylation of unactivated alkyl halides enabled by electrochemical reductive coupling is developed, affording a series of C(sp2)-C(sp3) products in moderate to good yields. This protocol proceeds in the absence of transition metal catalysts and redox mediators. The reaction features mild conditions, broad substrate scope, and high tolerance of functional groups and is demonstrated to be applicable for gram-scale synthesis and late-stage functionalization of natural products.