A series of new poly(1-vinyl-3-alkylimidazolium) iodide polymers with different alkyl derivatives such as methyl, propyl and perflurodecyl have been synthesized. The alkyl substituent influenced some properties such as solubility, thermal stability, glass transition and crystallinity of the polymers. For instance, polymer having the propyl substituent was soluble in solvents of intermediate polarity such as acetonitrile, chloroform and THF, the one with the methyl substituent was only soluble in very polar solvents such as water and methanol and the fluorinated polymer was only soluble in DMF. The alkyl substituent also influenced the thermal stability in the order methyl>propyl>perflurodecyl and all the polymers thermally decomposed between 250 and 400°C in nitrogen. The poly(1-vinyl-3-alkyl-imidazolium) iodide polymers having propyl and methyl substituents were amorphous polymers showing a glass transition temperature of 43 and 21°C, respectively; and perflurodecyl polymers were semi-crystalline with a Tm at 153°C and a Tg at 20°C, as indicated by differential scanning calorimetry. Polymer electrolytes were formulated as mixtures of the ionic liquid 1-methyl-3-propylimidazolium iodide and the poly(1-vinyl-3-alkylimidazolium) iodide polymers. These polymer electrolytes showed ionic conductivities in the range of 10−3 to 10−7 S/cm at room temperature which strongly depended on the ionic liquid content. Finally, poly(1-vinyl-3-propyl-imidazolium) iodide was used to obtain gel electrolytes by adding it to a typical acetonitrile electrolyte used in dye sensitized solar cells (DSSCs). Solar cells with 1cm2 area prepared using the polymer gel electrolyte yielded a maximum light-to-electricity conversion efficiency of 3.73%.