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The activity coefficient of Al in molten Cu decreases with the increasing of electric current applied to the liquid alloy of Cu-0.2wt%Al. To investigate the mechanism, the quenching experimental results of the liquid Al-Cu alloy show that there is a remarkable change in structure, in which the solute congregates along the current direction especially for DC current. The mechanism of the activity coefficient change of Al in molten Cu-0.2wt%Al alloy treated by electrical field was discussed. Further, the results also provide an evidence for the short-range-ordered liquid metal.