A broad range of functionalized aryl- and heteroarylzinc reagents were prepared via directed zincation of sensitive and moderately activated aromatics and heteroaromatics using TMPZnCl.LiCl under various reaction conditions. Diverse sensitive functional groups such as a nitro group, an aldehyde, an ester, and a nitrile are readily tolerated and are compatible with high metalation temperatures. Furthermore, the resulting zinc organometallics display an excellent reactivity toward various classes of electrophiles providing functionalized aromatics and heteroaromatics in high yields.