The operation of fusion reactors requires the development of a 6Li enrichment process that does not have a negative impact on the environment. This study focuses on a new two-liquid-phase chemical exchange system, liquid-metal/chloride molten salt system. In this system, 6Li is distributed unevenly between immiscible liquid metal and chloride molten salt. After two-liquid contacting mixing, a quadrupole inductively coupled plasma spectrometry measurement was performed. The measured isotope ratio of 6Li to 7Li was corrected with mass bias compensation, and separation factor α was obtained. In both systems (Li/LiCl-KCl system, and Li-Pb/LiCl-KCl system), the α values were greater than 1 at 648 K almost at a 68% confidence interval, showing that more 6Li was likely distributed to liquid metal than to chloride molten salt. These results suggest that this system is applicable to enrich 6Li under optimal temperature conditions.