This article reports the first fluorescent microparticles (MPs, approximately 600 nm in diameter) constructed using helical substituted polyacetylene and prepared via a precipitation polymerization approach. The MPs judiciously combine this interesting helical conjugated acetylene, fluorescent material and polymeric particles in one entity. The monomer containing a dansyl group undergoes precipitation polymerization in butanone/n‐heptane mixed solvent, with (nbd)Rh+B?(C6H5)4 as a catalyst. MPs with a regular morphology are formed in a high yield (>80 wt%). UV‐vis spectroscopy demonstrates that the polymer chains making up the MPs adopt helical structures. The MPs show considerable fluorescence emission (λmax, 500 nm; excited at 340 nm). Based on SEM and fluorescence images, the formation mechanism of the MPs is proposed. This methodology opens up new ways to prepare functional microstructured materials derived from substituted polyacetylenes, and may also result in opportunities for new practical applications of polyacetylene and its derivatives.