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Doping is an effective strategy for tailoring the optical properties of 0D Cs4PbX6 (X = Cl, Br, and I) perovskite nanocrystals (NCs) and expanding their applications. Herein, a unique approach is reported for the controlled synthesis of pure-phase Mn2+-doped Cs4PbCl6 perovskite NCs and the excited-state dynamics of Mn2+ is unveiled through temperature-dependent steady-state and transient photoluminescence (PL) spectroscopy. Because of the spatially confined 0D structure of Cs4PbCl6 perovskite, the NCs exhibit drastically different PL p