Site selectivity control is of vital importance in the direct functionalization of inert C–H bonds. Reported here is a novel example of remote regiodivergent ortho- and meta-C–H bond functionalizations of phenylethylamine derivatives by using a novel 2-cyanobenzoyl group as the original directing functionality, where the regioselectivity was adjusted by a methylation. The potential of the method was exemplified by sequential functionalizations of both ortho- and meta-C–H bonds of a phenylethylamine derivative in a streamlined manner.