In this study, we introduce polyacetylene-based polyelectrolyte for quasi-solid-state dye sensitized solar cells (DSSCs) applications. A conjugated polyelectrolyte was prepared via the phosphorus oxychloride-activated polymerization of 2-ethynylpyridine. Poly[2-ethynyl-N(dichlorophosphino) pyridinium chloride] was applied for DSSCs. The photoluminescence (PL) spectrum of polymer solution showed the two maximum peaks of 471 nm and 489 nm corresponding to the photon energy of 2.64 eV and 2.54 eV, respectively. Quasi-solid-state DSSCs with a SnO2:F/TiO2/D719dye/solid-state electrolyte/Pt device was fabricated with Poly[2-ethynyl-N-(dichlorophosphino)pyridinium chloride], which shows the maximum power conversion efficiency (PCE) of 5.70%.