In this publication a new synthesis approach of polyethersulfone containing sulfonimide groups (SI-PES), by chemical modification Of sulfonated polyethersulfone (S-PES), was developed. The synthesis protocol was optimized in order to turn all the sulfonic function into sulfonimide. The effect of replacing arylsulfonic acid function with a more acidic one, i.e. aryl trifluoromethanesulfonimide, was evaluated through thermal, dynamic mechanical analysis, water uptake and conductivity. For similar ionic exchange capacity (IEC), i.e. 1.8H(+)/dm(3), at 60 degrees C and 95% relative humidity, the conductivity of SI-PSF is 9.5 mS/cm while that of S-PSF is only 3.5 mS/cm. However, at 60 degrees C the water uptake is 3 times higher for SI-PSF membranes as compare with S-PSF. An important change is observed in the slope of the conductivity and water uptake plots of SI-PES membranes, at different temperatures, depending of IEC. This could be explained by an important change in membrane morphology. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.