A robust and efficient protocol for the introduction of the dioxolanylethyl moiety onto various aryl and heteroaryl halides has been developed, providing cross-coupling yields up to 93%. Copper-catalyzed borylation of 2-(2-bromoethyl)-1, 3-dioxolane with bis (pinacolato) diboron followed by treatment with potassium bifluoride provides the key organotrifluoroborate reagent.