A new, simple, and rapid separation and preconcentration procedure, for determination of Pb(II), Cd(II), Zn(II), and Co(II) ions in environmental real samples, has been developed. The method is based on the combination of coprecipitation of analyte ions by the aid of the Mo(VI)-diethyldithiocarbamate-(Mo(VI)-DDTC) precipitate and flame atomic absorption spectrometric determinations. The effects of experimental conditions like pH of the aqueous solution, amounts of DDTC and Mo(VI), standing time, centrifugation rate and time, sample volume, etc. and also the influences of some foreign ions were investigated in detail on the quantitative recoveries of the analyte ions. The preconcentration factors were found to be 150 for Pb(II), Zn(II) and Co(II), and 200 for Cd(II) ions. The detection limits were in the range of 0.1-2.2 mu g L-1 while the relative standard deviations were found to be lower than 5 % for the studied analyte ions. The accuracy of the method was checked by spiked/recovery tests and the analysis of certified reference material (CRM TMDW-500 Drinking Water). The procedure was successfully applied to seawater and stream water as liquid samples and baby food and dried eggplant as solid samples in order to determine the levels of Pb(II), Cd(II), Zn(II), and Co(II) ions.