Poly(ether ketone)s (PEK) containing 25-75 mol % valeric acid were prepared with bisphenol A, 4,4-dichlorobenzophenone and 4,4-Bis(4-hydroxylphenyl)valeric acid using potassium carbonate in DMAc (dimethyl acetami de) at 165 °C. Copolymers containing carboxylacid group were reduced to hydroxy group by BH3 solution 1M in THF and NaBH4 co-catalyst. Sulfonated poly(ether ketone)s (S-PEK) were obtained by reaction of 1,3-propanesultone and the reduced copolymer (PEK-OH) with sodium methoxide. A series of copolymers were studied by 1H-NMR spectroscopy, differential scanning calorimeter (DSC), and thermo gravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. The S-PEK membranes exhibited proton conductivities from 1.31 10-3 to 3.52 10-3 S/cm, water swell from 12.70 to 35.50 %, IEC from 0.45 to 0.75 meq/g and methanol diffusion coefficients from 3.65 10-7 to 5.10 10-7 cm2/S at 25 °C.