ABSTRACT Intrinsic luminescence in polymer hydrogels is highly desirable for soft optoelectronic and information‐security applications, yet remains difficult to achieve under hydrated conditions, where clusterization‐triggered emission (CTE) is easily quenched by water due to disrupted intermolecular interactions. Here, we establish a facile and general strategy to overcome this limitation via directional freezing‐assisted cryo‐polymerization. The anisotropic growth of ice crystals imposes spati