A plant operational status monitoring supervisory system comprising; means for extracting information directly relating to water quality of an objective portion consecutively for a period of time by means of an electrochemical water quality sensor installed in an objective portion to monitor in-situ in a plant; means for evaluating water quality based on thus extracted information; means for comparing an obtained water quality evaluation result with a reference value for a predetermined plant operation procedure; and means for displaying or storing necessary portion out of said comparison results; is disclosed.An electrochemical reference electrode used in this system being provided with an electrolyte layer containing ion of the electrode member; a porous ceramic layer surrounding the same without permeating liquid; and electrode member electrochemically contacting with said elec-trolyte layer; and a terminal electrically contacting with said electrode member; and further having a long life in high temperature water, various status of high temperature water in objective portions and that of nearby constituent members in a plant are possible to be monitored online by means of this reference electrode.Further, because monitored data are processed by means of a neural network, the higher precision level of monitoring has been achieved.