Quasi-solid-state dye-sensitized solar cells were fabricated using low-molecular-weight gelators. They showed comparable photoenergy conversion efficiencies to the liquid cell at high illumination intensity up to AM 1.5 (1 sun). Conductivity measurements of the electrolyte phases revealed that the gelation does not affect the conductivity of the electrolyte and that the conductivity increased with an increase of iodine in both gel electrolytes and liquid electrolyte. The formation of polyiodide ions, such as I-3(-) and I-5(-), caused by addition of iodine was confirmed by Raman spectroscopic measurement. The self-diffusion of iodide species in the gel electrolyte was found about a quarter of that of I- in acetonitrile. The formation of less-mobile polyiodide ions in electrolyte increased the conductivity in the mesoporous phase, which should be rationalized as due to the Grotthuss-type electron exchange mechanism caused by rather packed polyiodide species in the electrolytes. The optimized quasi -solid-state cell showed the values of 0.67 V for open-circuit voltage, 12.8 mA cm(-2) for short-circuit photocurrent density, and 5.91 % for photoenergy conversion efficiency under AM 1.5 irradiation with higher durability.