This article deals with the synthesis of sulfonated poly arylene ether ketones (SPEK-1 andSPEK-2) random copolymers via the direct copolymerization method as a polymer electrolyte membrane forfuel cell application. These copolymers were prepared via nucleophilic condensation reaction of 4,40-bis(4-hydroxyphenyl) valeric acid (DPA), dichlorobenzophenone (DCDPK), and sulfonated naphthalene/sulfonatedBPA monomers and characterized by FT-IR and 1H-NMR spectroscopic techniques. The crosslinking of thecarboxylic acid group bearing valeric acid was done by polyvinylalcohol (PVA) in order to obtain adimensionally stable membrane. The morphological and structural examination of the crosslinked membraneswas carried out by FT-IR, SEM, and XRD techniques. The fuel cell-related parameters such as water uptake,ion exchange capacity, proton conductivity, and oxidative stability were determined and have been discussedin this article.