A polymer gel electrolyte composed of a poly(ethylene oxide) derivative, poly(ethylene oxide-co-2-(2-methoxyethoxy) ethyl glycidyl ether), mixed with gamma-butyrolactone (GBL), LiI and I2 is employed in dye sensitized solar cells (DSSC). The electrolyte is characterized by conductivity experiments, Raman spectroscopy and thermal analysis. The influence of the electrolyte composition on the kinetics of DSSC is also investigated by transient absorption spectroscopy (TAS). The electrolyte containing 70 wt.% of GBL and 20 wt.% of LiI presents the highest conductivity (1.9 × 10−3 S cm−1). An efficiency of 4.4% is achieved using this composition. The increase in ISC as a function of GBL can be attributed an increase in the mobility of the iodide (polyiodide) species. The increase in the yield of the intermediate species, I2−, originating in the regeneration reaction, is confirmed by TAS. However, the charge recombination process is faster at this composition and a decrease in the Voc is observed. Photovoltage decay experiments confirm an acceleration in charge recombination for the DSSC assembled with the electrolyte containing more GBL. Raman investigations show that in this electrolyte the I5−/I3− ratio is higher. Theoretical calculations also indicate that the I5− species is a better electron acceptor.