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Mesoporous silica is one of the earliest and most mature mesoporous materials.It has broad application in the fields of adsorption separation, catalysis, drug loading and release, electrochemical sensor, nano reactor.The mesoporous silica/PVA nanofibers have the advantages of stable structure, large specific surface area, adjustable pore size, easy to carry out functional modification and good biocompatibility, more importantly, the gaps among the self supporting membrane fibers are beneficial to material and signal transmission, and is easy to be assembled into functional device.In this paper, the amino functionalization of mesoporous silica/PVA composite nanofibers was realized by the co synthesis surface modification method vis electrospinning, and the loading of the electrochemical active materials on the fibers and their electrochemical sensing properties were studied.The results showed that the morphology and the structure of the mesoporous silica fibers were affected by CTAB content, PVA content and aging time.The amino functionalized mesoporous silica/PVA nanofibers with a diameter of 200-650 nm, an average pore diameter of 2.89 nm within a narrow distribution, and a specific surface area of 656 m2g-1 were obtained.The electrode of amino functionalized mesoporous silica silicon/PVA fiber membrane can load phosphomolybdic acid to be a sensor and keep its electrochemical activity, which has a linear current response to different concentrations of BrO3-.