Copper-catalyzed cascade cyclization reactions between alkenyl boronic esters and N-H-based nucleophiles have been established, providing new approaches for one-pot assembly of azacycles. Following the Chan-Evans-Lam C-N couplings, the cyclization processes occur via divergent pathways based on the utilized substrates, affording hydroamination product dihydroquinazolin-4-ones or aromatization product quinolines. Via this one-pot C-N coupling/annulation cascade, the target substituted azacycles can be obtained in moderate to good yields in each case.