Poly(ethyleneoxide) (PEO) based gel network polymer electrolytes prepared from crosslinking reaction were applied in fabricating quasi-solid-state dye-sensitized TiO2 photoelectrochemical cells. Incident photon-to-current conversion efficiencies up to 48% and 40%, overall energy conversion efficiencies up to 3.6% and 2.9% have been achieved respectively for the resulting cells containing PEO2000 and PEO1500 segments.