The electron-catalyzed cross-coupling reaction of arylzinc reagents with aryl triflates was found to proceed under photoirradiation. Here arylzinc reagents undergo coupling with aryl triflates having an electron-donating or -withdrawing substituent. The studies on the reaction mechanism suggest that one of the driving forces of the carbon-carbon bond-forming step is a Lewis acid-base interaction between the metal center of arylzinc reagents and the leaving group of aryl electrophiles.