Abstract Organic room‐temperature phosphorescence (RTP) materials have attracted much attention in recent years due to their potential applications. However, the development of organic RTP emitters with a long lifetime and high quantum yield remains a great challenge owing to the weak molecular spin–orbit coupling and high sensitivity to oxygen. In this paper, a new purely organic RTP emitter, 3,3″,4,4″‐diphenylsulfonetetracarboxylic dianhydride (DPS), is reported which shows an excitingly ultralong lifetime up to 1.08 s and high phosphorescence quantum yield of 8%. When anhydride units in DPS are transformed into imides, the RTP performance in terms of lifetime and quantum yield is decreased. The presence of multiple intermolecular interactions is favorable for the restriction of nonradiative decay and the promotion of spin–orbit coupling, which is further corroborated by theoretical calculations. The studies demonstrate that DPS is a promising structural motif for developing high‐performance organic RTP emitters.