Facile and innovative route for large-scale synthesis of SiO2 fibers with excellent textural properties and H2O adsorption performance is presented. At first, a three-dimensional network of SiO2 precursor fibers was produced from tailored spun solutions (without any toxic elements and surfactants) by centrifugal spinning, which is a very modern fiber-synthesis technique, with numerous advantages over electrospinning. Upon thermal annealing of the precursor fibers, mesoporous amorphous SiO2 fibers with an ultrahigh surface area of up to 824 m2/g and pore size distribution in the range of 2-10 nm were produced. Owing to the high number of OH groups available on the surface, the produced SiO2 fibers showed significantly better performance in H2O adsorption compared to that of the reference silicagel.