The catalytic use of a sodium amide has been exploited for formal allylic C­(sp3)–H bond activation of alkenes under mild conditions. Subsequent C–C bond formations with imines have proceeded in high yields with complete regioselectivity and excellent geometric selectivity. Aromatic cyano, chloro, and bromo functionalities are tolerated by the transition metal-free catalyst. Complex amines bearing a CC double bond and distinct heteroaromatic units have been prepared in a single step. The critical importance of sodium versus other s-, p-, d-, and f-block metals as well as metal-free systems has been revealed. In addition, two catalytically active sodium-based intermediates were detected by NMR and HRMS analyses.