Metallurgical Transactions-and its subsequent MMTA and MMTB-has been a home for numerous contributions related to electrochemistry as it applies to solid, but also liquid materials. Herein, a perspective is presented to highlight the utility of electrochemical methods as applied to the study of liquid metals. The review of a subset of papers shows the diversity of experimental options available to investigate the thermodynamic properties of liquid metals, as well as certain limitations. A specific set of results covering the entire range of two liquid binary systems is reviewed as an illustration of the static electrochemical potential difference method. More recent developments offered by dynamic electrochemical potential methods, using direct and alternating currents or containerless configurations, are reviewed. Advances in electrochemical studies of liquid metals bring the prospect of simultaneous thermodynamic and transport properties measurements closer to reality.