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A new approach applying fuzzy mathematic theorems, including the Primary Matrix Element Theorem and the Fisher ClassificationMethod, was established to solve the optimization problem of atmospheric environmental sampling sites. According to its basis, an applicationin the optimization of sampling sites in the atmospheric environmental monitoring was discussed. The method was proven to be suitable andeffective. The results were admitted and applied by the Environmental Protection Bureau (EPB) of many cities of China. A set of computersoftware of this approach was also completely compiled and used.