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Abstract Blue phases (BPs), formed through the self‐assembly of chiral liquid crystal molecules into 3D nanolattices with cubic symmetries, exhibit dynamic photonic bandgaps in the visible spectrum, offering transformative opportunities for advanced optical circuits, sensing and communication technologies. However, their thermal stability is restricted to a narrow temperature range (0.5–1.0 K), limiting practical applications. Polymer stabilization of bulk BPs has extended thermal stability but often compromises the dynamic behavior essential for fast‐response functionalities. Here, experimental and computational approaches are integrated to investigate the effect of curvature and interfacial interactions on BP polymer stabilization. It is demonstrated that photo‐polymerization of reactive monomers within BP microdroplets produces polymer shells, a few hundred nanometers thick, featuring BPs disclination network nano‐architecture. This nano‐architected shell provides surface topology and anchoring conditions to direct BP nucleation and growth, with the degree of curvature dictating the stabilized BP lattice structure within microdroplets. Remarkably, while enhancing thermal stability across a broad temperature range, this polymer shell enables reconfigurable crystal‐to‐crystal transformations in stabilized BP droplets. This work introduces a novel approach to tailoring BP properties by leveraging curvature, confinement, and interfacial interactions to create thermally stable, reconfigurable photonic crystals, paving the way for adaptive sensors and next‐generation fast‐response optical devices.