The application of a polyaromatic acid–base blend membrane from partially fluorinated and sulfonated aromatic polyether and the polybenzimidazole F 6 PBI has been investigated for hydrogen production using SO 2 electrolysis. Several membrane electrode assembly (MEA) pre-doping strategies have been investigated using polarisation curves. Membrane thickness variation, voltage cycling and long term operation at constant current (0.1 A cm −2 ) was also performed. Scanning electron microscopy (SEM) and TGA-MS was used to evaluate MEA stability before and after long term operation. It was found that doping the MEA after hot pressing performs the best reaching a current density of 0.3 A cm −2 . The performance could also be improved by cycling the voltage 16 times to reach 0.33 A cm −2 . Long term operation showed stable voltage at 0.1 A cm −2 staying below 0.8 V. SEM images showed that no significant sulfur deposition was present while TGA-MA analysis confirmed some degradation after the 140 h of operation.