From an ecological and economical point of view, it is important to design analytical procedures for monitoring heavy metals in the environment and industrial processes in a way to minimize the use of hazardous reagents and reduce the analysis time. In this paper, a well-known dithizonate extraction-based method for the determination of many metal ions was improved by using chemometrical selectivity of the strongly overlapped spectra of copper and cadmium dithizonates in CCl4 for their simultaneous determination from a single extraction at pH 10. The individual absorption spectra, having absorption maxima difference of only 20 nm, were separated, and the metal ions were quantified by using an improved procedure for optimizing the resolving function in a recently proposed signals ratio method. The procedure consists of using many different resolving functions and plotting the difference of the mean of absolute and nonabsolute mean values of pseudosignals [PDMMV (PS)] against analyte concentrations obtained with each of the resolving functions, thus obtaining 2 straight lines having intersections that give a unique and reliable value of the unknown concentration of the individual analyte in mixture giving strongly overlapped spectra. In this way, the main drawback of the signals ratio resolution method, that is, the visual estimation of optimal resolving function, is eliminated. The proposed parameter, PDMMV (PS), was tested by using both simulated and experimental spectra. Copper was determined in the mixture with ca 20-fold excess of cadmium, and cadmium was determined in ca 10-fold excess of copper at submicromolar concentration levels.