Photonic crystals (PCs) have been widely applied in optical, energy, and biological fields owing to their periodic crystal structure. However, the major challenges are easy cracking and poor structural color, seriously hindering their practical applications. Now, hydrophobic poly(tert‐butyl acrylate) (P(t‐BA)) PCs have been developed with relatively lower glass transition temperature (Tg), large crack‐free area, excellent hydrophobic properties, and brilliant structure color. This method based on hydrophobic groups (tertiary butyl groups) provides a reference for designing new kinds of PCs via the monomers with relatively lower Tg. Moreover, the P(t‐BA) PCs film were applied as the photoluminescence (PL) enhanced film to enhance the PL intensity of CdSe@ZnS QDs by 10‐fold in a liquid‐crystal display (LCD) device. The new‐type hydrophobic force assembled PCs may open an innovative avenue toward new‐generation energy‐saving devices. A tert‐butyl acrylate (t‐BA) monomer for the construction of hydrophobic P(t‐BA) photonic crystals toward magnetic‐optics displays and energy saving devices is presented. It may open an innovative avenue toward the assembled PC field.