A process for rapid synthesis of 4-acetoxyindoles from readily available 2-alkynylanilines was reported. The process involves an oxidative dearomatization and subsequent cascade nucleophilic addition/cyclization/aromatization. A range of functional groups can be tolerated in this process. The formed 4-acetoxyindoles are versatile precursors to a variety of C4-functionalized indoles through simple conversions.