This work investigates the ion conduction of polymer electrolytes confined in cylindrical pores having diameters ranging from 400 to 30 nm. The confinement of PEO polymer electrolytes in nanopores increases ionic conduction as the pore size decreases with the greatest conductivity occurring in pores that were 30 nm in diameter where a specific conductivity of 2.43×10−4 S cm−1 was observed. This is almost two orders of magnitude higher than a polymer electrolyte film of the same composition but not confined in nanopores. This enhanced conduction may occur because of an orientation of the polymer chains in the pores. In addition to the advantage of enhanced conduction, these membranes have enhanced conduction perpendicular to the plane of the thin electrolyte film, which is the configuration desired for the construction of polymer electrolyte films for use in batteries.