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Porous shape‐persistent organic cages have become the object of interest in recent years because they are soluble and thus processable from solution. A variety of cages can be achieved by applying dynamic covalent chemistry (DCC), but they are less chemically stable. Here the transformation of a salicylimine cage into a quinoline cage by a twelve‐fold Povarov reaction as the key step is described. Besides the chemical stability of the cage over a broad pH regime, it shows a unique absorption and emission depending on acid concentration. Furthermore, thin films for the vapor detection of acids were investigated, showing color switches from pale‐yellow to red, and characteristic emission profiles.

A Robust Porous Quinoline Cage: Transformation of a [4+6] Salicylimine Cage by Povarov Cyclization