A novel kind of supramolecular liquid‐crystalline polymer (SLCP) microparticles was successfully fabricated with an azopyridyl polymer and sebacic acid by combining a simple self‐organized precipitation method with hydrogen bonding interactions. Upon slow evaporation of a mixed solution of a volatile good solvent and a nonvolatile poor one, walnutlike microparticles showing wrinkled surfaces and LC natures were obtained. The diacid might play a crucial role in the formation of SLCP particles. Without addition of the diacid, neither wrinkled surfaces nor LC natures were observed in azopyridyl polymer microparticles. The fabricated SLCP microparticle possessed not only photoresponsive properties (due to azopyridyl groups) but also LC ordering, which might enable them to find advanced applications.
