Ru(II)-catalyzed condition-controlled divergent coupling between 3-aryl-2H-benzoxazin-2-ones and benzoquinones has been realized under operationally simple conditions, affording a series of structurally stable spiropyrans and valuable arylquinones. The potential of this method is also demonstrated by scale-up synthesis and derivatization. Additionally, an unprecedented cycloruthenated complex has been identified as a key intermediate.