A nickel(II)-catalyzed addition of aryl-, alkenyl-, and alkylboronic acids to alkenylazaarenes was presented. This reaction exhibited high efficiency (up to 93% yield), a broad substrate scope (seven types of heterocycles), and good functional group compatibility. The resulting products can be further transformed to many useful building blocks. Finally, the preliminary studies suggested that the adjacent N atom of the heterocycles was essential for the high reactivity.