A kind of pi-conjugated poly(EDOT-ethynylene-arylene)s P1-P5 were synthesized by Sonogashira coupling reaction between DBEDOT and five arylenes substituted with ethynyl groups. Among them, P5 was a polymer with TTF as pendants. Their TGA results exhibited their good thermal stability and their electrochemical and spectroscopic properties were investigated by CV, UV-Vis, and FL. The results indicated that there were intramolecular interactions between TTF group and polymer backbone as well as between the EDOT and arylene moieties. After doping with TCNQ, P5 could form stable CT-complex with a conductivity of 1.3 x 10(-3) S cm(-1), while its conductivity could be up to 3.5 x 10(-2) S cm(-1) after doping with I-2, due to its increased conductive dimensions. Such results indicated that this polymer had potential application in developing conducting materials. A kind of pi-conjugated EDOT-ethynylene-fluorene polymer with TTF as pendants was synthesized, which exhibited good solubility and thermal stability. When doping with I-2, its conductivity was improved significantly due to its increased conductive dimensions.