In the present study, we examine the water and proton transport properties of hexafluorinated sulfortated poly(arylenethioethersulfone) (6F-SPTES) copolymer membranes for applications to proton exchange membrane fuel cells (PEMFCs). The 6F-SPTES copolymer membranes build upon the structures of previously studied sulfonated poly(arylenethioethersulfone) (SPTES) copolymer membranes to include CF3 functional groups in efforts to strengthen water retention and extend membrane performance at elevated temperatures (above 120 degrees C. The 6F-SPTES copolymer membranes sustain higher water self-diffusion and greater proton conductivities than the commercial Nalion (R) membrane. Water diffusion studies of the 6F-SPTES copolymer membranes using the pulsed-field gradient spin-echo NMR technique reveal, however, the fluorinated membranes to be somewhat unfavorable over their non-fluorinated counterparts as high temperature membranes. In addition, proton conductivity measurements of the fluorinated membranes up to 85 degrees C show comparable results with the non-fluorinated SPTES membranes. (C) 2007 Elsevier B.V. All rights reserved.