AbstractPolyether ether ketone (PEEK) with a low sulfonation degree was blended using different proportions of sodium rich Smectite clay (3 and 6 wt%) to use as an electrolyte membrane for fuel cell application. The structural functionalities, surface morphologies, and the thermal stability of the resultant composite membranes were characterized using Fourier‐transform infrared spectroscopy, X‐ray diffraction (XRD), scanning electron microscopy, atom force microscopy, and thermo‐gravimetric analysis. FT‐IR showed that no chemical reactions take place between the sulfonated polyether ether ketone (SPEEK) and the clay with different ratios. XRD diffractograms illustrated a lower degree of crystallinity of the blended SPEEK than pristine SPEEK. The elaborated composite membranes proved to have a higher thermal stability than SPEEK. Furthermore, the SPEEK/clay composite membranes with 3 and 6 wt% in clay loading had higher water uptake and lower methanol uptake than those in pristine SPEEK It was also shown that, the incorporation of sodium ions rich Smectite clay layers between the clusters in SPEEK improved the conductivity to 2 × 10−2 S/cm at 140°C (for 6 wt% in clay) without compromising the dimensional stability of the composite membranes. These results propose the composite membranes as a potential candidate for methanol fuel cells at temperatures above 120°C making SPEEK composite membrane competitive to that of Nafion membrane.