Highly crystalline mesoporous zirconia fibers with high surface area have been prepared by the use of electrospinning combined with precursors method. The obtained precursor fibers were treated in water steam and directly in air at different temperature respectively. Compared with the direct calcination in air, the water steam cannot only promote the crystallization of ZrO2 but also effectively remove off the organics and prevent the pore structure collapse. Moreover, through adding hydrochloric acid to modify the solution pH value, the obtained t-ZrO2 fibers treated in water steam at 300 degrees C have high surface area and large pore volume of 232.70 m(2)g(-1) and 0.36 cm(3) g(-1). The formation mechanism of the mesostucture was studied and the schematic was represented. Compared with the previous reports of mesoporous ZrO2 fibers, the as-synthesized materials exhibited the high crystallinity, large surface area and the long-range order mesostructure. The adsorption of Congo red indicates that the samples have a high adsorption capacity of 103.46 mg g(-1) and long-periodic repeated availability. (C) 2016 Published by Elsevier B.V.