Homoallylic amines are important synthetic targets in organic synthesis. Compared to other conventional allylation reactions using pre-functionalized allylic compounds, the allylation of imines using alkenes represents an attractive strategy to access homoallylic amines, especially in terms of atom- and step-economy. Here we report that a dicationic Cp*Co-III catalyst efficiently promotes the allylation reactions of aliphatic imines with simple terminal alkenes under mild reaction conditions. The allylation reactions would proceed via an imino-ene type mechanism, inwhich the Cp*Co-III catalyst works as a Lewis acid.