The development of polymeric materials with novel structures and unique properties and functionalities is of both academic and industrial significance. In this work, functional poly(dihalopentadiene)s were synthesized by boron trihalide-mediated multicomponent polymerization routes in a stereoselective manner. The polymerizations of tetraphenylethylene-containing diyne, BX₃ (X = Cl, Br) and -tolualdehyde proceed smoothly in dichloromethane under mild conditions to afford high molecular weight poly(dihalopentadiene)s with a predominant (,)-configuration in moderate to good yields. The reaction conditions and the boron trihalide used were found to have great effects on the stereochemistry of the resulting polymer structures. The obtained poly(1,5-dihalo-(,)-1,4-pentadiene)s possess high thermal stability and good film-forming ability. Their thin films show high refractive index of 1.9007⁻1.6462 in a wide wavelength region of 380⁻890 nm with low optical dispersion. The polymers are weakly emissive in dilute solutions but become highly emissive upon aggregated, demonstrating a unique phenomenon of aggregation-enhanced emission. Their nanoaggregates in aqueous media can serve as sensitive fluorescent chemosensors for the detection of explosives with a superamplification effect and a low detection limit.