A series of poly (arylene ether ketone sulfone) s containing different amino content (Am-PAEKS) were prepared via direct polycondensation reactions, and then the sulfobutyl groups were grafted onto the Am-PAEKS by amidating reaction between the amide groups in Am-PAEKS and carboxylic acid groups in 4-(N-butane sulfonic) aminobenzoic acid. The structures of the compounds and the polymer were confirmed by FTIR and H-NMR. The new characteristic bands at 1 239 and 1 060 cm-1 were assigned toOSO symmetric stretching vibration and asymmetric stretching vibration of the sulfonic groups in sulfonated poly (arylene ether ketone sulfone) on side chain (S-SPAEKS), and the structures of the polymers were further confirmed by 1H NMR spectra, and the proton peak at 1.64 ppm was assigned to the methyl in the middle of the pendant sulfonated aliphatic side chains, which show that the S-SPAEKS had been prepared successfully. In TGA curves we can observe two distinct weight loss steps, the first step was mainly attributed to the splitting-off of the sulfonic acid groups at 300 ℃, and the second step was mainly attributed to the decomposition of the main chain of the S-SPAEKS at 450 ℃. This series of S-SPAEKS polymers exhibit excellent thermal properties by thermo gravimetric analysis, which can satisfy the basic requirements of proton exchange membrane (PEM) for fuel cells.