A soluble anion exchange ionomer with high OH− ion conductivity comparable to that of H+ conductivity of Nafion is synthesised by chloromethylation of polystyrene-b-poly (ethylene/butylene)-b-polystyrene (SEBS) and used with NiCo2O4 electro-catalyst for water electrolysis. The ionomer has an ion exchange capacity of 1.9 mmol g−1 and ionic conductivity of 0.14 S cm−2 at 50 °C. The cell voltage at 20 °C at 100 mA cm−2 is 1.77 and 1.72 V in, 0.1 and 1.0 M NaOH, respectively, for an optimum loading of 10 mg cm−2 NiCo2O4. At 10 mg cm−2 NiCo2O4 electrolyser cell performance is at least equal to or superior to that of IrO2 at 2 mg cm−2 with excellent stability over 1 h. When the catalyst is sprayed on the GDL instead of CCM, the performance is further improved to 1.65 V at 100 mA cm−2 at 60 °C & 0.1 M KOH. The limited AEM electrolyser performance when operating with deionised water in comparison to PEM and alkaline electrolyser arises from the sluggish OER in the AEM environment equivalent to pH of 11.5 and the two orders of magnitude lower HER activity with respect to acid medium combined with the high Tafel slope of 120 mV dec−1.