Cerium and its compounds are widely used in the production of electronic devices and semiconductors, which is why these substances will enter the environment more often in the future. There is a need for effective express methods that can determine the trace amounts of cerium and other rare earth elements with high accuracy to control and study the possible negative impact of cerium compounds on the ecosystems. The objective of this research paper was to elaborate on an express method capable of producing accurate and reliable results on the content of cerium in wastewaters in the presence of other rare earth elements. The elaboration of the express method was carried out based on the amperometric titration method studying the effect of various buffer solutions on cerium determination. Moreover, the effect of strontium, lutetium, iron, yttrium, samarium, niobium, holmium, praseodymium, gadolinium, and erbium ions on acquisition accuracy of the cerium (III) ions in samples of process water was studied. The research results presented a method for the amperometric determination of cerium (III) applying 2,7-dinitroso-1,8-dihydroxynaphthalene-3,6-disulfonic acid on a rotating platinum disk microelectrode. The extraction-amperometric method of analysis was proposed for the analysis of process water. The optimal concentrations of background electrolytes and buffer mixtures and the voltage values, were determined; the stability constant of the complex was calculated; the lower limit of the determined cerium content was defined. No interfering influence of foreign ions on the determination of cerium (III) ions was observed. The developed method for determining cerium (III) has a simpler hardware design than the previously described method of pulsed direct current glow discharge mass spectrometry but has a higher detection limit.