An efficient Rh‐catalyzed aminative dearomatization of naphthols was achieved. In the presence of Rh2(esp)2 and HOSA as an inexpensive and readily available aminating reagent, a series of unprotected α‐amino‐β‐naphthalenones was afforded in good yields under mild reaction conditions. This reaction features good tolerance of functional groups and multi mmol‐scale reaction.