Mesoporous alumina fibers were successfully synthesized via an electrospinning technique combined with a sol-gel method in the presence of a triblock copolymer as a structure directing agent. The amorphous alumina fibers derived from the electrospun xerogel fibers after calcinations at 450 degrees C and the gamma-Al2O3 fibers obtained after the xerogel fibers were calcined at 700 degrees C exhibit uniform mesopores with fiber diameters of 130-200 nm, and BET surface areas up to 264.1 m(2) g(-1) and 242.6 m(2) g(-1), respectively. After the xerogel fibers were calcined at 1100 degrees C, with the transformation from gamma-Al2O3 to alpha-Al2O3, a significant grain growth occurs and the mesopores disappear. Further investigation indicates that the gamma-Al2O3 fibers have good adsorption properties toward Congo red with a maximum adsorption capacity of 781.25 mg g(-1) for the sample obtained at 700 degrees C. In addition, the fibers show a good stability in acidic conditions and during a reuse process, which indicates their potential applications in adsorption as well as related areas, such as catalysis and catalyst supports.