A Cu-mediated/catalyzed selective oxidative dual C–H bond cleavage of an arene and alkylnitrile or acetone is reported. This method provides a novel approach to highly functionalized fluorene and pyrroloindole derivatives, which are useful in pharmaceutical and photoelectronic areas. In this reaction, two new C(sp³)–C(sp³) and C(Ar)–C(sp³) bonds, a quaternary center and a five-membered ring are simultaneously formed.