A series of copolymers P(VP-HEMA) composed of hydroxyl ethyl methacrylate (HEMA) and 4-vinyl pyridine (VP) were prepared by a solution copolymerization technique. Based on the copolymer P(VP-HEMA) prepared by the content of VP 50%, the amount of AIBN 3% and the optimized liquid electrolyte, a polymer solution electrolyte with concentration of 9.0% was formed. By addition of 1,4-dibromobutane into the solution, the copolymer gel electrolyte with higher conductivity 6.14mS/cm was prepared. Gelation is caused by the quaterisation between the group of pyridine in P(HEMA-VP) and 1,4-dibromobutane. Based on the copolymer gel electrolyte, a dye-sensitized solar cell was fabricated with short-circuit current of 13.62mA/cm2,open circuit voltage of 0.72V, fill factor of 0.5465 and an overall conversion efficiency of 5.24% under irradiation 100mW/cm2(AM1.5).