Abstract Photocurable electrolytes were prepared by mixing proton-conductive polymer sulfonated poly(ether ether ketone) (SPEEK), cross-linking monomer divinyl sulfone (DVS), photoinitiator phenylbis(2,4,6-trimethylbenzoyl)phosphineoxide (PI), dimethylacetamide (DMA), and ethanol. To investigate the proton transport property, a series of photocurable electrolytes with various PI content ratios were prepared to form photocured membranes. Water uptake, ion exchange capacity (IEC), proton conductivity, and water-resistance of the photocured membranes were investigated. Water-resistant photocured membrane is easy to prepare, which gives relatively high proton conductivity (28 mS cm − 1 under 70 °C and relative humidity of 90%). Patterning of micro-structure on the photocured membrane was also demonstrated by using the property of the photocurable electrolytes.