Herein, by exploiting different activation modes of fluoroamides, we achieved α- and δ-C(sp3)-H alkylation of nitroalkanes with switchable regioselectivity. Cu catalysis enabled the interception of a distal C-centered radical by a N-centered radical to couple nitroalkanes and unactivated δ-C-H bonds. In addition, imines generated in situ by fluoroamides were trapped by nitroalkanes to realize the α-C-H alkylation of amides. Both of those scalable protocols have broad substrate scopes and good functional group tolerance.