C(sp3)-H bond nitration provides facile access to nitro compounds that are inaccessible through traditional nitration pathways. This work describes a C(sp3)-H bond nitration of aryl alkenes using DNDMH, a nitration reagent developed previously in our lab. Notably, this novel nitration process presents excellent regioselectivity and chemoselectivity between C(sp3)-H nitration and C(sp2)-H nitration.