Several polymers containing triphenylene moieties in main chain were synthesized by Knovenagel or Wittig condensations. The polymers were characterized by 1 H NMR, IR, GPC, TG, UV–vis, FL and CV. Results indicated that PNB, which was prepared from the polycondensation of 4,4′-dialdehyde-4″-n-butyltriphenylamine with 1,4-bis(triphenylphosphonionmethyl)benzene dibromide, is the most thermally stable one and that PNP, which was prepared from the polycondensation of 4,4′-dialdehyde-4″-n-butyltriphenylamine with p-phenylene diacetonitrile, is the most thermally instable one. The fluorescence quantum efficiency of PNB is 94.3%, which is a high value for optoelectronic polymer materials. All the polymers have a similar CV curve with a reversible oxidation peak and two reduction peaks except that PNB has a single reduction peak.