A general catalytic base-controlled regiodivergent nucleophilic hydrofunctionalization of both terminal and internal β,γ-unsaturated amides has been reported. The atom-economical addition of various S/P-based nucleophiles was also exclusively chemoselective. More than 60 branched or linear hetero-substituted aliphatic amides were synthesized from common starting materials under transition-metal-free conditions. Preliminary mechanistic studies are consistent with our proposed divergent catalytic cycles.