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Transmission XAFS measurements were performed on lanthanum chloride (LaCl 3 ) and LaCl 3 -Li 2 O mixture at various temperatures using La-K X-ray absorption edge. A distinct phase shift in the EXAFS oscillations was observed in going from the solid phase to the molten phase in LaCl 3 . The results of curve fitting to the predominant peak in the structure function of LaCl 3 in real space, corresponding to the La 3+ -Cl − 1st coordination shell, reveal that both the interionic distance and coordination number of chloride ions around a lanthanum ion decreased with increase in temperature to above its melting point. The short-range structure of LaCl 3 -Li 2 O (x Li 2 O = 5 mol%) mixture appears to be almost similar to that observed in pure LaCl 3 .