A coupling between various alkynylstannanes with a-iodo esters was catalyzed by GaBr3 under UV irradiation conditions, for which a catalytic amount of GaBr3 was essential, and a radical coupling with the generated alkynylgallium species was involved. The desired alpha-alkynyl esters were selectively obtained even in the presence of an aryl-I bond, which is a reactive site in a conventional palladium-catalyzed system.