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Application of the fundamental parameter method to quantitative analysis of slags and rocks was studied. The program used for calculation is XRF-11. Pressed powder samples after screening at 44μm and glass beads of the dilution ratio (sample + flux/sample) of 11 were used for analysis of slags, and glass beads of the dilution ratio of 5 were used for analysis of rocks. Accuracies for each component obtained from the fundamental parameter method were equal to those from the calibration curve method except for the minor components in the powder samples and glass beads. The proposed method showed good reproducibility in slag and rock analysis. The relative standard deviation was in the range of 0.271.23% for each component in the slags and 0.231.78% in the rocks.