Abstract Complex non‐equilibrium phase behaviors are a hallmark of natural self‐assembling systems. Here we show how intricate phase transitions can be achieved through a chemically fueled reaction cycle to yield autonomous sol→gel→sol→gel→sol transitions. A relay of chemical transformations based on thiazinane metathesis leads to two consecutive transient gelations in a closed system. Within seconds of fuel addition to deactivated thiazinane monomers, an imine‐based hydrogel forms that consists of fibrillar microspheres. This gel quickly loses its mechanical strength and forms a solution, from which a second aldehyde‐based gel nucleates and remains stable for over one day. Overall, our reaction cycle gives rise to two consecutive re‐entrant phase transitions without any experimental intervention.
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