We report a copper-catalyzed aminoheteroarylation of unactivated alkenes to access valuable heteroarylethylamine motif. The developed reaction features a copper-catalyzed intermolecular electrophilic amination of the alkenes followed by a migratory heteroarylation. The method applies to alcohol-, amide-, and ether-containing alkenes, overcoming the common requirement of a hydroxyl motif in previous migratory difunctionalization reactions. This reaction is effective for the introduction of diverse aliphatic amines and has good functional group tolerance, which is particularly useful for rich functionalized heteroarenes. This migration-involved reaction was found well suited as a powerful ring-expansion approach for the construction of medium-sized rings that are in great demand in medicinal chemistry.