<p>Block copolymer (BCP) photonic crystals (PCs) have great potential in color decoration, optical encryption, and smart sensing because of their excellent flexibility and stimuli-responses. Supramolecular BCPs (SBCPs) provide a versatile platform for engineering structural colors through reversible non-covalent interactions, yet their precise dynamic modulation under confined environments remains underexplored. Here, we develop an integrated real-time monitoring system to elucidate the temperature-solvent synergistic annealing strategy to regulate the disorder-to-order transition of hydrogen-bonded comb-like SBCPs and homopolymers binary co-assembly system, which can yield a lamellar structure and exhibit structural color. Systematic investigation revealed that increasing solvent content accelerates ordering kinetics and induces a red-shift of structural color in their swollen states, while the equilibrium structural color remains solvent-independent upon solvent removal. Unexpectedly, elevating the temperature decelerates ordering kinetics and induces a blue-shift in both swollen and dry states. This counterintuitive phenomenon can be attributed to thermally reduced solvent uptake (by SBCPs) and partial hydrogen-bond dissociation, diminishing the molecular weight and rigidity of SBCPs. These findings elucidate the critical role of swelling and dynamic hydrogen-bond interactions in governing assembly pathways, structure and optical properties of SBCPs, providing a versatile platform for designing stimuli-responsive PC materials with on-demand colors and color switching.</p>