We report the synthesis of novel fluorinated ionic polyacetylenes by spontaneous polymerization of 2-ethynylpyridine (2-EP) with trifluoroacetic acid (TFA), heptafluorobutyric acid (HFBA) and pentadecafluorooctanoic acid (PDFOA) without any initiator or catalyst. The activated polymerization of the acetylenic bond in 2-EP with fluorinated carboxylic acids resulted in substituted, conjugated ionic poly acetylenes bearing protonated pyridinium side groups. The reactions of 2-EP and fluorinated carboxylic acids were observed to be faster than 2-EP with alkyl halides. The high acidity of FCA was an important factor in the activated polymerization. In contrast with the fluorinated acids, 2-EP did not polymerize with acetic acid due to the low efficiency of weaker acidity of common carboxylic acids on the activated mechanism. The fluorinated ionic polyacetylenes, poly(2-ethynylpyridinium trifluoro acetate) (P2EPF), poly(2-ethynylpyridinium heptafluorobutylate) (P2EPH) and poly(2-ethynylpyridinium pentadecafluorooctanoate) (P2EPP) were analyzed by various characterization techniques such as Fourier transform infra-red spectroscopy, nuclear magnetic resonance, ultra-violet visible light spectrometer (UV-Vis), photoluminescence spectrometer (PL) and X-Ray diffraction. The UV-Vis absorption spectrum of the P2EPP solution showed higher conjugated polymer backbones than P2EPF and P2EPH. The PL spectrum of the FIPA solution in DMSO displayed two bands centered at 510 and 560 nm, whose fluorescence peak positions were similar. The counter ion effect of the fluorinated carboxylates affected the polymer solubility in organic solvents. The electrochemical property of the fluorinated ionic polyacetylenes was investigated by cyclic voltammetry, which revealed good stability.