Blend membranes based on sulfonated polyetheretherketone (SPEEK) and containing 5 wt.% of silylated and sulfonated polyphenylsulfone (SiSPPSU) were prepared and characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATRJFTIR) and by electrochemical impedance spectroscopy (EIS). Tests in a direct methanol fuel cell station were also performed. The experimental results demonstrated that the presence of hybrid polymer SiSPPSU allowed to increase the proton conductivity of electrolyte and to improve its performance under fuel cell operating conditions. Due to its satisfactory properties, SPEEK! SiSPPSU blend membrane has a potential use in DMFCs operating at intermediate temperatures.