A new series of sulfonated poly(benzoxazole ether ketone)s (SPAEKBO-X) were prepared by the aromatic nucleophilic polycondensation of 4,4'-(hexafluoroisopropylidene)-diphenol with 2,2'-bis[2-(4-fluorophenyl)benzoxazol-6-yl]hexafluoropropane and sodium 5,5'-carbonylbis-2-fluorobenzenesulfonate in various ratios. Fourier transform infrared and H-1 NMR were used to characterize the structures and sulfonic acid contents of the copolymers. The copolymers were soluble in N-methyl-2-pyrrolidinone, NN-dimethylacetamide, and NN-dimethylformamide and could form tough and flexible membranes. The protonated membranes were thermally stable up to 320 degrees C in air. The water uptake, hydrolytic and oxidative stability, and mechanical properties were evaluated. At 30-90 degrees C and 95% relative humidity, the proton conductivities of the membranes increased with the sulfonic acid content and temperature and almost reached that of Nafion 112. At 90-130 degrees C, without external humidification, the conductivities increased with the temperature and benzoxazole content and reached above 10(-2) S/cm. The SPAEKBO-X membranes, especially those with high benzoxazole compositions, possessed a large amount of strongly bound water (>50%). The experimental results indicate that SPAEKBO-X copolymers are promising for proton-exchange membranes in fuel cells, and their properties might be tailored by the adjustment of the copolymer composition for low temperatures and high humidity or for high temperatures and low humidity; they are especially promising for high-temperature applications. (C) 2007 Wiley Periodicals, Inc.