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The internal and external overvoltage in distribution networks is the main reason of accidents. Based on overvohage data in distribution network recorded by overvoltage on-line monitoring system, this paper analyzes the characteristics of zero sequence voltage waveform. The maximum amplitude and RMS value of zero sequence voltage, the minimum RMS of low frequency component of three phase voltage in stable range and other five parameters are selected as characteristic parameters to identify internal and external overvoltage. According to the operation data and record, all overvohage data recorded by on-line monitoring system were labeled as internal or external overvoltage and the discrimination function is constructed by support vector machine method. The test results of field acquired overvohage data indicate that the identification parameters and method based on the zero sequence voltage and support vector machine (SVM) are correct and effective.