Fabrication of iodine-free and heat tolerant solid-state dye-sensitized solar cells (DSC) will be presented. DSC faces low (>-40°C) to high (<85°C) temperature stability issue to pass standardized packaging durability tests of solar cells. One of the solutions is the fabrication of DSC without using iodine-containing volatile electrolytes. PEDOT, poly (3,4-ethylenedioxythiophene) works as an excellent hole conducting polymers, being successfully used as an substitute of the liquid I-/I3- redox electrolytes in DSC. In this work we cleared the in-situ photoelectropolymerization technique to synthesize PEDOT in mesoscopic TiO₂ anodes, and carried out a careful analysis of the effect of ionic liquid-derived anions on overall solar cell performance. The ionic liquid anions analyzed in this work were bistrifluoromethanesulfonylimide anion (TFSI-), ClO4-, CF3SO3-, BF4-, and the best solar cell performance was obtained when the TFSI- anion was used. Photo-electrochemical and impedance studies revealed that the doped anions in the PEDOT hole conductor system have great influences on I-V curves, conductivity, and impedance. The optimization of these parameters allowed us to obtain an iodine-free solid state DSC with a maximum Jsc of 5.3 mA/cm2, Voc of 750 mV and a conversion efficiency of 2.85%, which is the highest efficiency obtained so far for an iodine-free PEDOT-based DSC.