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The liquid structure of iron-rich Fe-Si alloys (the silicon content is 22, 32, 34, 50 at%, respectively) was studied by high temperature θ-θ diffractometer at 1 550 ℃. The results show that the coordination number of atoms decreases with increasing silicon content. A visible pre-peak was observed in the structure factor of Fe-Si alloys, especially for the liquid Fe78Si22 and Fe68Si32 alloys. The special study was given on the liquid structure of Fe68Si32 alloy at temperature from 1 250 to 1 550 ℃. A distinct pre-peak was found at scattering vector Q=15.5 nm-1 in the structure factor. That means there are ordered D03 structure clusters in the liquid Fe68Si32 alloy. The correlation between silicon atoms in the Fe3Si compounds leads to the pre-peak in the structure factor.