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Organic red/near‐infrared (NIR) room temperature phosphorescence (RTP) materials with low toxicity and facile synthesis are highly sought after, particularly for applications in biotechnology and encryption. However, achieving efficient red/NIR RTP emitters has been challenging due to the weak spin‐orbit coupling of organics and the rapid nonradiative decay imposed by the energy gap law. Here we demonstrate highly efficient red/NIR RTP with boosted quantum yields (Φps) of up to 32.96 % through doping the thionated derivatives of phthalimide (PAI) (MTPAI and DTPAI) into PAI crystals. The red‐shifted photoluminescence (PL) stems from a combination of the external heavy atom effect and the formation of emissive clusters centered around electron‐rich sulfur atoms. Furthermore, the dopants enhance exciton generation efficiency and facilitate energy transfer from smaller PAI units to larger aggregates, leading to dramatically increased Φp. This strategy proves universal, opening possibilities for acquiring long‐wavelength RTP with tunable photophysical properties. The doped crystals exhibit promising applications in optical waveguides and encryption paper/ink. This research provides a practical approach to obtaining long‐wavelength RTP materials and offers valuable insights into the mechanisms governing host‐guest systems. [ABSTRACT FROM AUTHOR]