Novel single-ion conducting polymer electrolytes based on electrospun poly(lithium 2-acrylamido-2-methylpropanesulfonic acid) (PAMPSLi) membranes were prepared for lithium-ion batteries. The preparation started with the synthesis of polymeric lithium salt PAMPSLi by free-radical polymerization of 2-acrylamido-2-methylpropanesulfonic acid, followed by ion-exchange of H+ with Li+. Then, the electrospun PAMPSLi membranes were prepared by electrospinning technology, and the resultant PAMPSLi fiber-based polymer electrolytes were fabricated by immersing the electrospun membranes into a plasticizer composed of ethylene carbonate and dimethyl carbonate. PAMPSLi exhibited high thermal stability and its decomposition did not occur until 304°C. The specific surface area of the electrospun PAMPSLi membranes was raised from 9.9 m2/g to 19.5 m2/g by varying the solvent composition of polymer solutions. The ionic conductivity of the resultant PAMPSLi fiber-based polymer electrolytes at 20°C increased from 0.815 × 10−5 S/cm to 2.12 × 10−5 S/cm with the increase of the specific surface area. The polymer electrolytes exhibited good dimensional stability and electrochemical stability up to 4.4 V vs. Li+/Li. These results show that the PAMPSLi fiber-based polymer electrolytes are promising materials for lithium-ion batteries. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012