Poly(ether sulfone)s (PES) containing 25-75 mol % valeric acid were prepared with bisphenol A, bis(4-chlorophenyl)sulfone and 4,4-Bis(4-hydroxylphenyl)valeric acid using potassium carbonate in DMAc (dimethylacetamide) at 160 °C. Copolymers containing carboxylacid group were reduced to hydroxy group by BH3 solution 1M in THF and NaBH4 co-catalyst. Sulfonated poly(ether sulfone)s (S-PES) were obtained by reaction of 1,3-propanesultone and the reduced copolymer (PES-OH) with potassium t-butoxide. A series of copolymers were studied by 1H-NMR spectroscopy, differential scanning calorimetry (DSC), and thermo gravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. The S-PES membranes exhibited proton conductivities from 1.20 10-3 to 3.40 10-3 S/cm, water swell from 12.25 to 31.50 %, IEC from 0.43 to 0.72 meq/g and methanol diffusion coefficients from 3.60 10-7 to 4.90 10-7 cm2/S at 25 °C.