A solvent-free polymer electrolyte and a secondary battery employing the electrolyte are provided. The electrolyte includes: a porous film, including a first polymer and a second oligomer, the first polymer being at least one selected from the group consisting of poly (vinylidene fluoride-co-hexafluoropropylene) copolymers, polyvinylidenefluorides, polymethylmethacrylates, polyacrylonitriles, polyethyleneoxides, and celluloses having a polyether chain, and the second oligomer being at least one selected from the group consisting of poly(ethylene oxide-co-ethylene carbonate) copolymers with at least one terminal groups substituted by a halogen atom and polyethyleneglycols with at least one terminal group substituted by a halogen atom. An electrolyte comprising the second oligomer and a lithium salt is present in the pores of the porous film.