The first 6π-photocyclization of dienynes was developed, which provides a new and effective protocol for the synthesis of the phenyl ring in excellent yields with nice functional group tolerance. In this transformation, the Cu(OTf)2 catalyst plays a key role in the conversion of alkyne moiety into an alkene-type moiety, which means that the dienyne reactant is converted into a triene-type substrate. Thus, this reaction proceeds via a Cu(II)-catalyzed 6π-photocyclization of triene-type derivatives.