In order to improve the proton conductivity of hollow silica spheres (HSS)/perfluorosulfonic acid ion-exchange (PFSA) composite membranes as proton exchange membrane,sulfonic acid groups were grafted onto the surfaces of HSS via post grafting methods.TEM images and FT-IR spectra of the obtained sulfonic acid groups modified hollow silica spheres (SAMHSS) illustrated that the sulfonic acid groups were successfully grafted onto the surfaces of HSS.Water uptake and swelling degree of SAMHSS/PFSA composite membranes were found much higher than those of HSS/PFSA membranes due to the introduction of hydrophilic sulfonic acid groups.In a range from 50 ℃ to 130 ℃,the highest conductivity of composite membranes was obtained when 5 wt% SAMHSS was loaded.The maximum conductivity reached 7.5×10-2 S·cm-1 at 100 ℃ and 100% relative humidity,even the temperature increased to 130 ℃,the conductivity of composite membranes with 5 wt% SAMHSS could reach 3.7×10-2 S·cm-1 at 100 % relative humidity,while the conductivity of the recast PFSA was only 2.2×10-3 S·cm-1.