The [4 + 2] cycloaddition of styrenes with arynes was achieved via 1:1 cross-coupling by a nickel catalyst. This protocol applies to a variety of styrenes and arynes generated in situ from o-(trimethylsilyl)aryl triflates to afford 9,10-dihydrophenanthrenes involving substituted aromatic rings. By using this method, a naturally occurring stilbenoid is easily synthesized.