Highly branched photoluminescent polyphenylenes (PP) containing 1,3,5-triphenylbenzene (TPB) fragments were prepared via combination of cyclocondensation of acetylaromatic compounds and Ni0-catalyzed dehalogenation. Defect free PP with star-like fragments were synthesized using Ni0-catalyzed polymerization of aromatic bromides obtained by modification of 1,3,5-tri(p-bromophenyl)benzene. The molecular weights of the polymers were 6700, 8600, and 15300 Da. The maximum photoluminescence in solution (quantum yield of 96%) was obtained for the highly branched polymer with star-like TPB fragments, bearing no Br or acetyl groups. The PP of this kind show also very bright fluorescence in a solid state under UV irradiation at 360 nm so they can be considered as promising materials for OLED applications.