To develop ion-exchange membranes for application in severe conditions, such as those with high temperatures, strongly oxidizing environments, or organic solvents, new hollow-fiber anion-exchange hybrid membranes were prepared by the immersion of brominated poly(2,6-dimethyl-1,4-phenylene oxide) base hollow fibers in a tetraethoxysilane-ethanol Solution followed by sol-gel and quaternary amination. Compared to conventional polymeric charged membranes, the prepared hybrid membranes were higher in both thermal and dimensional stabilities. The results suggest that tetraethoxysilane concentration was an important factor affecting the membrane's intrinsic properties. When the tetraethoxysilane concentration was in the range 15-45%, the final hollow-fiber anion-exchange hybrid membranes had an ion-exchange capacity of 1.9-2.0 mmol/g, a water uptake of 83-1.23 g of water/g of dry weight, and a dimensional change ratio of 13-18%. An evaluation on the membranes' separation performances is underway. (C) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 111: 3128-3136, 2009