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Recent studies were reviewed on the PIXE analysis of metal ions preseparated by means of capillary type isotachophoresis (ITP-PIXE). The principle was described of isotacho-phoresis which was one of electrophoretic methods with high separability and concentration ability. Some applications of ITP-PIXE were demonstrated on the investigation of the separation behavior of metal ions and the analysis of trace elements in a crude rare earth chloride from a monazite and a model mixture of a high level liquid waste. It was revealed that PIXE could be a powerful detection method for the fractions of isotacho-phoresis because of its high sensitivity and multielemental analyzability. Since the matrix effect in X-ray measurement was significantly reduced by such preseparation, the minor elements could be determined accurately.