Linear, α‐branched, and β‐branched aliphatic amines are widespread in pharmaceuticals, agrochemicals, and fine chemicals. Thus, the development of direct and efficient methods to these structures in a tunable manner is highly desirable yet challenging. Herein, a catalyst‐controlled synthesis of α‐branched, β‐branched and linear aliphatic amines from Ni/Co‐catalyzed regio‐ and site‐selective hydroalkylations of alkenyl amines with alkyl halides is developed. This catalytic protocol features the reliable prediction and control of the coupling position of alkylation to provide orthogonal access to α‐branched, β‐branched and linear alkyl amines from identical starting materials. This platform unlocks orthogonal reactivity and selectivity of nickel hydride and cobalt hydride chemistry to catalytically repurpose three types of alkyl amines under mild conditions. A unified protocol for Ni/Co‐catalyzed remote and regiodivergent hydroalkylations of alkenyl amines has been established, providing orthogonal access to α‐branched, β‐branched, and linear aliphatic amines. This catalytic protocol features the reliable prediction and control of the coupling position of alkylation to provide orthogonal access to aliphatic amines with diverse scaffolds from identical starting materials.