A new type of π-conjugated polymers containing 2-diisopropylamino-1,3,5-triazine were prepared via Sonogashira or Suzuki coupling reaction. The structures of the polymers were performed by FT-IR, 1H-NMR, UV–vis spectroscopy, photoluminescence spectroscopy, gel permeation chromatography, thermal analysis and X-ray diffraction analysis. These derived polymers were soluble in common organic solvents such as tetrahydrofuran, chloroform, toluene, and showed good thermal stability. Polymers containing 1,4-diethynyl-2,5-bis(dialkoxy)benzene unit in polymer main chain emitted blue-green light in solution phase under UV light irradiation except with polymer containing 9,9-dioctylfluorene(blue light). Acidochromic behaviors of polymers were studied in CHCl3-CF3COOH mixtures. 9,9-Dioctylfluorene-containing polymer displayed better acidochromic property and linear relationship between absorbance and concentration with the concentration of CF3COOH from 5.384 × 10−4 to 26.92 × 10−4 mol/L. Electrochemical behaviors of polymers depicted p-doping and some hole-transporting properties. XRD results showed that polymers exhibited certain crystallinity.