LAUSR

Abstract 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 properties of Mn2+ in comparison with their 3D CsPbCl3 analogues, including significantly improved PL quantum yield in solid form (25.8%), unusually long PL lifetime (26.2 ms), large exciton binding energy, strong electron–phonon coupling strength, and an anomalous temperature evolution of Mn2+‐PL decay from a dominant slow decay (in tens of ms scale) at 300 K to a fast decay (in 1 ms scale) at 10 K. These findings provide fundamental insights into the excited‐state dynamics of Mn2+ in 0D Cs4PbCl6 NCs, thus laying a foundation for future design of 0D perovskite NCs through metal ion doping toward versatile applications.