High molecular weight, hyperbranched polyarylenes were synthesized in high isolation yields by the copolycyclotrimerizations of 2,5-diethynylthiophene (1), 4,4′-biphenyldiyne (2), and 2,7-diethynylfluorenes (3) with 1-heptyne (4) and 1-dodecyne (5) using TaCl₅-Ph₄Sn as the catalyst in toluene. The structures of the polymers were characterized by IR, NMR, TGA, and UV analyses. All the polymers exhibited outstanding thermal stability and emitted strong blue light, whose intensities are higher than that of poly(1-phenyl-1-octyne), a well-known highly emissive polyacetylene. Little red shift was observed in the photoluminescence of the polymer thin films. The polymers strongly attenuated intense pulses of 532 nm laser pulses.