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A simple and mild photoredox catalytic approach to access difluoroalkylated dioxodibenzothiazepines in high regioselectivity via radical cascade cyclization has been described herein. In contrast to previous methods, this strategy does not involve the use of transition-metal catalysts and avoids the potential disadvantages of inevitable toxicity and the tedious removal process of metal catalysts. The commercially available and inexpensive CF2 precursors, wide substrate scope, and mild reaction conditions demonstrate the practicability of this approach.