Confining luminophores into modified hydrophilic matrices or polymers is a straightforward and widely used approach for afterglow bioimaging. However, the afterglow quantum yield and lifetime of the related material remain unsatisfactory, severely limiting the using effect especially for deep‐tissue time‐resolved imaging. This fact largely stems from the dilemma between material biocompatibility and the quenching effect of water environment. We herein present an in situ metathesis promoted doping strategy, namely, mixing ∼10−3 weight ratio of organic‐emitter multicarboxylates with inorganic salt reactants, followed by metathesis reactions to prepare a series of hydrophilic but water‐insoluble organic‐inorganic doping afterglow materials. This strategy led to the formation of edible long‐afterglow photoluminescent materials with superior biocompatibility and excellent bioimaging effect. The phosphorescence quantum yield of the materials can reach dozens of percent (the highest case: 66.24%), together with the photoluminescent lifetime lasting for coupes of seconds. Specifically, a long‐afterglow barium meal formed by coronene salt emitter and BaSO4 matrix was applied into animal experiments by gavage, and bright stomach afterglow imaging was observed by instruments or mobile phone after ceasing the photoexcitation with deep tissue penetration. This strategy allows a flexible dosage of the materials during bioimaging, facilitating the development of real‐time probing and theranostic technology.This article is protected by copyright. All rights reserved