A novel gel network polymer electrolyte based on polysiloxane with internal plasticizing PEO chains was applied in fabricating solid-state dye-sensitized TiO2 photoelectrochemical cells. Ethylene carbonate (EC)/propylene carbonate (PC) and LiI/I-2 were added as liquid plasticizer to improve the performance. The cells showed open circuit voltage of 0.69 V and short circuit current density of 1.7 mA cm(-2) under 28 mW cm(-2) white light illumination. The energy conversion efficiencies and fill factors of the cells were 2.9% and 0.72.