A new conjugated ionic polymer was applied for DSSCs. Poly(2-ethynyl-N-methylpyridinium iodide) (PEMPI) was prepared by the non-catalyst polymerization of 2-ethynylpyridine using iodomethane without any additional initiator or catalyst. The polymerization proceeded homogeneously to give a high yield of polymer (87%). The photoluminescence peak was observed at 568nm corresponding to a photon energy of 2.19eV. Quasi-solid-state DSSCs with a SnO2:F/TiO2/D719 dye/solid-state electrolyte/Pt device was fabricated with PEMPI, which shows the maximum power conversion efficiency (PCE) of 6.01%.