With a view towards direct methanol fuel cell applications, novel sulfonated poly(phenylene sulfide sulfone nitrile) (sPPSSfN) has been prepared and subsequently crosslinked by a Friedel‐Craft reaction using 4,4′‐oxybis(benzoic acid) as a crosslinker to achieve lower water swelling and lower methanol permeability. The dimensional change of SPPSSfN40 is 43.7% in 90 °C liquid water but that of the crosslinked membrane, XsPPSSfN40, is 23.3% while maintaining proton conductivity at 0.22 S · cm−1. These results show that the Friedel‐Craft crosslinking of the novel sPPSSfN membrane effectively reduces water uptake and the degree of swelling while improving the dimensional stability and maintaining high proton conductivity.