A simple and efficient AgOTf-promoted tandem olefin isomerization/intramolecular hydroamination of 1,1-disubstituted alkenyl amines has been developed. This one-pot process represents a facile and attractive route for the synthesis of diverse 2-alkyl-substituted 1,3-X,N-heterocycles through chemo- and regioselective C(sp3)-N bond formation with atom economy. Advantages such as the operationally simple and practical procedure that uses a readily available catalyst under aerobic conditions, good to excellent chemical yields, the high functional group tolerance, the broad substrate scope, and high efficiency and selectivity are noteworthy.