Abstract: To establish a rapid, accurate and non-destructive method for the inspection of leather shoe soles by SEM / EDS, 56 samples of different leather shoes soles were discriminated by SEM / EDS.The samples were preliminarily classified according to SEM and EDS. The exact classification of the samples was realized by chemometrics and the SEM / EDS model to distinguish the model of sole of leather shoes was established. The results show that the shoe soles can be tested qualitatively by SEM/EDS. The method is sensitive, convenient and reproducible, and can be used to identify shoe sole materials.