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The vulnerability is property that the structure and function of system are easy to be destroyed after certain external disturbances. The status of vulnerability study on water resources system at present has been pointed out. A new vulnerability assessment index system has been established. A fuzzy clustering method is used to evaluate the vulnerability classification of water resources system. An integrated analysis method is adopted to calculate different index weights. The example operates vulnerability classification towards districts of Shanxi Province's water resources system in 2004 year. The vulnerability classification results demonstrate that vulnerability of water resources in Shanxi Province is high commonly in 2004. The proportions of the three grade serious vulnerability area, middle vulnerability area and feeble area of Shanxi Province's water resources system are 63.64%, 9.09% and 27.27% in 2004 year respectively. The conclusions are consistent with the reality of Shanxi Province.