Here, we developed an air-stable, earth-abundant cobalt(III)-catalyzed regioselective mono-olefination of arenes directed by urea under mild conditions through a cross-dehydrogenative coupling (CDC) process. Under the optimized conditions, a high regioselectivity of mono-olefination was achieved with various electron-rich and electron-deficient arenes, which afforded E-alkenylated products (with yields of up to 90%). In contrast to the conditions used for noble-metal-catalyzed olefination directed by weakly coordinating groups, our reaction was operated under mild conditions, including mild temperature (40 °C) and non-metallic oxidant.