The optimum degree of sulfonation (DS) for sulfonated poly(ether ether ketone) (SPEEK) membranes is determined by comprehensive characterization results, including proton conductivity, swelling ratio, water uptake, chemical stability, thermal stability, mechanical indicators, and proton exchange membrane fuel cell (PEMFC) performance. The PEMFC with a membrane electrode assembly containing a SPEEK-62 (DS = 62%) membrane realizes the power density of 482.08 mW/cm², surpassing that of commercial Nafion-212 under identical conditions. In the crucial Fenton test for durability, the SPEEK-51 membrane demonstrated outstanding dimensional and chemical stability, with a decomposition time of up to 137 min, far surpassing the durability of SPEEK-62 or other membranes with a higher DS. The results indicate that in comparison to the SPEEK-67 membrane as reported in the literature, SPEEK membranes with a DS = 51~62% hold great potential for future applications in PEMFC, and further modifications of these membranes can be a promising approach to enhance the conductivity while maintaining good chemical stability.