A program involving the design, construction, and operation of a high-temperature cell equipped with a rotating gold disk electrode has been carried out with the objective of identifying and quantifying the principal oxide species present in molten LiKCO/sub 3/ electrolytes using electrochemical measurements. The dependence of the current on electrode rotational speed at 750 to 800/sup 0/C indicates that the data are typical of the convective/diffusive transport of an electroactive species from the bulk electrolyte. The reverse is true at 650/sup 0/C, where the current increases with an increasing voltage sweep rate but is little affected by the speed of electrode rotation. In the latter case, a current by chemical reaction occurring within the electrode boundary layer is indicated. The linear current-voltage increase observed at the lower temperature in the presence of about 20 mol % 0/sub 2/ has not been accounted for. Graphical analysis of the data taken with air and C/sub 2/ sparged electrolyte at 750 and 800/sup 0/C indicates the electroactive species to be the superoxide ion. Computer studies of the same data using regression analysis methodology indicate that the current may instead arise from the reduction of the peroxide ion concurrently with other electroactive material derived from secondary catalytic reactions or electrolyte impurities. Additional data will be required to support either conclusion with certainty. Detailed studies of the electrochemistry of the LiKCO/sub 3/ electrolyte over a broader range of temperatures and sparge gas compositions are recommended as a means of providing a second basis for identifying the electrode reactions. 29 refs., 47 figs., 3 tabs.