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A composite Nafion‐TiO2 membrane was manufactured by a recast procedure, using an in‐house prepared TiO2. This membrane has shown promising properties for high temperature operation in an SPE electrolyser allowing to achieve higher performance with respect to a commercial Nafion 115 membrane. This effect is mainly due to the water retention properties of the TiO2 filler. A promising increase in electrical efficiency was recorded at low current densities for the composite membrane‐based SPE electrolyser at high temperature compared to conventional membrane‐based devices.