Polymeric lithium salts of sulfonated polysulfone (SPSU(X)Li) were synthesized via post sulfonation route followed by ion exchange. A novel single ion conducting solid polymer electrolyte (SPE) was prepared by curing poly(ethylene glycol)diglycidyl ether (PEGDGE) with 4,4' diaminodiphenyl sulfone (DDS) in SPSU(X)Li matrix. The ionic conductivity, thermal stability and tensile properties were investigated as a function of degree of sulfonation and PEGDGE concentration. The introduction of lithium sulfonate groups in polysulfone promoted compatibility of SPSU(X)Li and PEGDGE in SPE. AFM analysis demonstrated heterogeneous phase morphology and reduction in size of dispersed PEGDGE phase with increasing degree of sulfonation. The interactions between lithium sulfonate and polyether epoxy improved thermal stability of the epoxy network. The enhanced compatibility also caused improvement in elongation at break compared to neat SPSU(X)Li. The higher Li+ ion concentration and the segmental mobility of the polymer chains above T-g contributed to the high ionic conductivity at high temperature in the single ion conducting SPE. (c) 2009 Elsevier Ltd. All rights reserved.