The design of a radical relay chaperone to promote selective C-H functionalizations is described. A saccharin-based imine was found to be uniquely suited to effect C-H amination of alcohols via an in situ generated hemiaminal. This radical chaperone facilitates the mild generation of an N-centered radical while also directing its regioselective H atom transfer (HAT) to the β carbon of an alcohol. Upon β C-H halogenation, aminocyclization, and reductive cleavage, an NH2 is formally added vicinal to an alcohol. The development, synthetic utility, and chemo-, regio-, and stereoselectivity of this imine chaperone-mediated C-H amination is presented herein.